TW201131615A - Multilayer mirror for euv lithography and process for producing same - Google Patents
Multilayer mirror for euv lithography and process for producing same Download PDFInfo
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- 238000001900 extreme ultraviolet lithography Methods 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000010410 layer Substances 0.000 claims abstract description 292
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 192
- 239000011241 protective layer Substances 0.000 claims abstract description 132
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 130
- 239000012298 atmosphere Substances 0.000 claims description 88
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 65
- 230000003746 surface roughness Effects 0.000 claims description 34
- 230000036961 partial effect Effects 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000005855 radiation Effects 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 18
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000001459 lithography Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001659 ion-beam spectroscopy Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000007687 exposure technique Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- -1 nitrogen or argon Chemical compound 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002680 soil gas Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
- G03F1/24—Reflection masks; Preparation thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0891—Ultraviolet [UV] mirrors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70216—Mask projection systems
- G03F7/70316—Details of optical elements, e.g. of Bragg reflectors, extreme ultraviolet [EUV] multilayer or bilayer mirrors or diffractive optical elements
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
- G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/70983—Optical system protection, e.g. pellicles or removable covers for protection of mask
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Environmental & Geological Engineering (AREA)
- Public Health (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Mathematical Physics (AREA)
- Theoretical Computer Science (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Optical Elements Other Than Lenses (AREA)
- Optical Filters (AREA)
Abstract
Description
201131615 六、發明說明： 【發明戶斤廣之技術嘴域】 發明領域 本發明係有關於一種在半導體製造等所使用之 EUV(EXtreme Ultraviolet ;極紫外線)微影術用多層膜鏡（以 下，在本說明書，稱為「EUVL用多層膜鏡」）及其製造方法。 C先前技冬好J 發明背景 先前，在半導體產業，作為有關在矽基板等形成由微 細圖案構成的積體電路所必要的微細圖案之轉印技術，係 一直應用使用可見光和紫外光之微影術法。但是，半導體 元件的微細化係越來越加速，逐漸接近先前的微影術法之 限度。微影術法之情況，圖案的解像限度係曝光波長的1/2 左右，即便使用浸液法，一般認為係曝光波長的1/4左右， 且即便使用ArF雷射（193nm)的浸液法係預測45_左右為 限度。因此，作為使用比45nm短曝光波長之下世代的曝光 技術，使用比ArF雷射更短波長的£UV光之曝光技術亦即 EUV微影術係被認為是有希望的。在本說明書，所謂EUV 光係指軟X射線區域或是真空紫外線區域的波長之光線，具 體上係指波長1〇〜2〇nm左右、特別是13 5nm±〇 3nm左右的 光線。 因為EUV光係對所有物質均容易被吸收，且物質在該 波長的折射率係接近1，所以無法使用如先前使用可見光或 紫外線的微影術這種折射光學系。因此，EUV光微影術係 201131615 使用反射光學系亦即反射型光罩及鏡。 在EUV微影術所使用的鏡’係具有在玻璃製等的基板 上形成反射EUV光的反射層之構造。作為反射層，由於能 夠達成高EUV光線反射率’故通常係使用使高折射層與低 折射率層交替地積層複數次而成之多層反射膜。因此，作 為在EUV光微影術所使用的鏡，通常係使用在此種基板上 形成多層反射膜而成之多層膜鏡(參照專利文獻1)。 為了保護多層反射膜避免化學性、物理性侵害之目 的，此種多層膜鏡係多半在該多層反射膜上形成有保護$ (保護蓋層）。 在專利文獻1所記載的多層膜鏡之情況，係具備保護蓋 層，該保護蓋層係由自釕(Ru)及铑(Rh)與選自該等的化合物 或合金中之材料所構成。 先前技術文獻 專利文獻 專利文獻1:日本特許第4068285號公報說明書 【發明内容】 發明概要 發明欲解決之課題 在EUVL用多層膜鏡的多層反射膜，通常係使用 多層反射膜，該Mo/Si多層反射膜係使用作為低折射率層之 鉬(Mo)層、及作為高折射率層之矽(Si)層而成。 在EUVL用多層膜鏡的保護層之材料，基於即便對保護 層表面照射EUV光時亦能夠得到高反射率，而以使用^^為佳。 4 201131615 但是，使用Ru作為保護層的材料時，在製造該多層膜 鏡所實施的步驟(例如洗淨步驟、加熱步驟等）中，或是在使 用EUV光微影術之EUV曝光時，由於Ru保護層、甚至多層 反射膜的最上層（Mo/Si多層反射膜時為Si層）被氧化，而有 對保護層表面照射EUV光時之EUV光線反射率低落的可能性 之問題。 特別是因為EUV曝光時的EUV光線反射率低落係經時 性進行，產生在途中變更曝光條件之必要，或產生更換 EUVL用多層膜鏡之必要，牵連到EUVL用多層膜鏡的壽命 縮短而造成問題。 以下，在本说明書，有將在製造EUVL·用多層膜鏡時所 實施的步驟(例如洗淨步驟、加熱步驟等），或是在使用Euv 光微影術之EUV曝光時’由於RU保護層、甚且多層反射膜 的最上層被氧化，致使對保護層表面照射EUV光時之euv 光線反射率低落，簡稱為「由Ru保護層的氧化引起之EUV 光線反射率低落」之情形。 鑒於上述情形，本發明係將提供一種經抑制由Ru保護 層的氧化引起之EUV光線反射率低落之EUVL用多層膜鏡 及其製造方法設作目的。 用以欲解決課題之手段 為了解決上述課題，本發明者等專心研討的結果，發 現藉由在Mo/Si多層反射膜與Ru保護層之間，形成含有預定 量的氮及Si之中間層，能夠抑制由ru保護層的氧化引起之 EUV光線反射率低落。 201131615 本發明係基於上述本發明者等的知識而進行，提供__ 種EUV微影術用多層膜鏡(EUVL用多層膜鏡），其係在基板 上依照順序形成反射EUV光的反射層、及保護該反射層的 保護層而成之EUV微影術用多層膜鏡，其特徵為： 前述反射層為Mo/Si多層反射膜， 前述保護層為Ru層、或Ru化合物層，並且 在前述反射層與前述保護層之間，形成含有0.5〜 25at%的氮且含有75〜99.5at%的Si之中間層。 前述由Mo/Si多層反射膜所構成的反射層之最上層係 以Si膜為佳，且前述中間層係鄰接該以膜而形成為佳。 在本發明的EUVL用多層膜鏡中，前述中間層的膜厚度 係以0.2〜2_5nm為佳。 在本發明的EUVL用多層膜鏡中，前述保護層表面的表 面粗链度rms係以0.5nm以下為佳。 在本發明的EUVL用多層膜鏡中，前述保護層的膜厚度 係以1〜1 Onm為佳。 又，本發明係提供一種半導體積體電路之製造方法， 其特徵為藉由使用上述本發明的EUVL用多層膜鏡對被曝 光體進行曝光來製造半導體積體電路。 又’本發明係提供一種EUV微影術用多層膜鏡之製造 方法’其係藉由在基板的成膜面上形成反射EUV光之多層 反射膜後’在前述多層反射膜上形成該多層反射膜的保護 層’來製造EUV微影術用多層膜鏡(EuvL用多層膜鏡）之 EUVL用多層膜鏡之製造方法，其特徵為： 201131615 前述多層反射膜為Mo/Si多層反射膜， 前述保護層為Ru層、或Ru化合物層，並且 形成前述Mo/Si多層反射膜後，將該Mo/Si多層反射膜 的最上層亦即Si層表面不曝露於大氣中而是曝露於含氮氣 體環境，使Si層表面含有氮後，形成前述保護層。 在本發明的EUVL用多層膜鏡之製造方法中，以前述含 氮氣體環境之氮分壓（Torr)與曝露時間（s)的乘積為 lxlCT6Torr.s(=1.33><10-4Pa.s)=lL(Langmuir))以上且該含氮 氣體環境的溫度為0〜170°C為佳。 在本發明的EUVL用多層膜鏡之製造方法中，以前述含 氮氣體環境之氮分壓（Torr)與曝露時間（s)的乘積為 lxl〇-6Torr.s以上且該含氮氣體環境的溫度為0〜160°C為較 佳。 在本發明的EUVL用多層膜鏡之製造方法中，以前述含 氮氣體環境之氮分壓（Torr)與曝露時間（s)的乘積為 lxlO_6Torr*s以上且該含氮氣體環境的溫度為0〜150°C為更 佳。 就促進在Si層表面含有氮而言，在本發明的EUVL用多 層膜鏡之製造方法中，將前述Si層表面曝露在含氮氣體環 境時，係以將前述含氮氣體環境保持在電漿狀態、或是熱 處理該Si層表面、或是對該Si層表面照射紫外線為佳。 發明效果 本發明的EUVL用多層膜鏡，能夠抑制由Ru保護層的氧 化引起之EUV光線反射率低落。而且，依照本發明的製造 201131615 方法’能夠製造經抑制由RU保護層的氧化引起反射率降低 之EUVL·用多層膜鏡。又，本發明的EUV微影術用多層膜 鏡’因為能夠抑制EUV光線反射率低落，故能夠有效地利 用於製造半導體積體電路，特別是能夠以良好生產效率製 造具有微細圖案之半導體積體電路。 圖式簡單說明 第1圖係顯示本發明EUVL用多層膜鏡的實施形態之概 略剖面圖。 C實施方式;J 用以實施發明之形態 以下’參照圖式來說明本發明。 第1圖係顯示本發明EUVL用多層膜鏡的一實施形態之 概略剖面圖。第1圖所表示的EUVL用多層膜鏡1，係在基板 11上依照順序形成反射EUV光的反射層12、及用來保護該 反射層12的保護層14。但是，本發明的EUVL用多層膜鏡係 在反射層12與保護層14之間，形成含有後述預定量的氮及 Si之中間層13。 以下說明EUVL用多層膜鏡1的各自構成要素。 基板11係滿足作為EUVL用多層膜鏡用的基板之特性。 因此，基板11具有低熱膨脹係數係重要的。具體上， 基板11的熱膨脹係數係以〇±1.〇Χ1〇-7Λ：為佳，以〇±〇_3xl(T7/ 。(：為較佳，以〇±〇·2χΐ〇-7Α：為更佳，以〇±〇」><1〇-7/芄為又更 佳，以0±0.05xl(r7/eC為特佳。又，基板係以具有平滑性、 及對EUVL用多層膜鏡的洗淨等所使用的洗淨液之耐性優 201131615 良者為佳。作為基板11，具體上係使用具有低熱膨脹係數 之玻璃、例如Si〇2-Ti〇2系玻璃等，但是不被此限定，亦可 使用析出点石英固溶體之結晶化玻璃、或石英玻璃、或矽 或金屬等的基板。又，亦可在基板11上形成如應力修正膜 的膜。 因為在EUVL用多層膜鏡能夠得到高反射率，故基板11 係以具有表面粗糙度rms為0.15nm以下的平滑表面為佳。 基板11的大小和厚度等係可藉由鏡的設計值等來適當 地決定。 基板11係以在形成有多層反射膜12之側的表面不存在 缺點為佳。 EUVL·用多層膜鏡的反射層12所要求的特性係高EUV 光線反射率。具體上，對反射層12表面以入射角度6度照射 EUV光的波長區域之光線時，波長13.5nm附近的光線反射 率的最大值係以60%以上為佳，以65%以上為更佳。又，在 反射層12上即便設置有中間層13及保護層14時，在波長 13.5nm附近的光線反射率的最大值亦是以60%以上為佳， 以65°/。以上為更佳。 因為在EUV波長區域能夠達成高反射率，故作為EUVL 用多層膜鏡的反射層，係廣泛地使用將高折射率膜與低折 射率層交替地複數次積層而成之多層反射膜。 本發明的EUVL用多層膜鏡係使用Mo/Si多層反射膜， 該Mo/Si多層反射膜係以使作為低折射率層的Mo層及作為 高折射率層的Si層交替地複數次積層而成為佳。 201131615 在該Mo/Si多層反射膜，被積層的M〇/Si多層反射膜之 最上層係以設作Si膜為佳。 屬Mo/Si多層反射膜時’欲做出EUV光線反射率的最大 值為60%以上的反射層12 ’可將膜厚度為2 3；t〇 lnm的Mo層 及膜厚度4.5±0.1nm的Si層以重複單位數為3〇〜60的方式積 層即可。 又，構成Mo/Si多層反射膜之各層，係使用磁控管濺鍍 法、離子射束濺鍍法等眾所周知的成膜方法，以成為所需 要的厚度之方式進行成膜即可。例如，使用離子射束賤鑛 法形成Mo/Si多層反射膜時，作為標靶係使用Mo標靶，作 為踐鍍氣體係使用Ar氣體（氣壓l.3xl(r2pa〜2.7xl0-2Pa)，離 子加速電壓為300〜1500V、成膜速度為〇,〇3 〜0.30nm/sec， 且以厚度成為2.3nm的方式將Mo層成膜，隨後，作為標靶 係使用si標靶、作為濺鍍氣體係使用Ar氣體（氣壓為 1·3χΐ pa〜2.7xi(r2pa) ’離子加速電壓為3〇〇〜15〇〇v、成 膜速度為0.03〜0.30nm/sec，且以厚度成為七允爪的方式將 Sl層成膜為佳。將此作為i周期，並藉由使M〇層及si層積層 40〜50周期來將Mo/Si多層反射膜成膜。 本發明的EUVL用多層膜鏡係藉由在反射層12與保護 層14之間形成含有〇 5〜25如％的氣且含有75〜99 5扣〇/。的^ 之中間層13 ’來抑制^Ru保護層的氧化引起EUV光線反射 率低落。藉由在反射層12與保護層Μ之間形成上述組成的 中間層13 ’能夠抑制由Ru保護層的氧化引起EUV光線反射 率低落之理由係推測如下。 201131615 上述組成的中間層丨3係為了避免產生因在反射層12最 上層的S! ”Ru保護層的氧化而含有大量的氧致使反射率 降低’於是使中間層13減含有氮’藉此成職的反射率 问且具有抑制氧化之效果。藉此，即使在EUVL用多層膜鏡 製造時所實施的步驟(例如洗淨、缺陷檢查、加熱步驟、缺 等的各步驟）中、或是在EUV光顯微術的EUv曝光 時，產生如;RU保護層被氧化的狀況，因為具有抑制氧化效 果之中間層13的存在，而能夠抑制在該中間層13下方之 M〇/Sl夕層反射膜被氧化，更具體地，能夠抑制在Mo/Si多 層反射膜的最上層的Si層被氧化。其結果，推測能夠抑制 由Ru保護層的氧化引起EUV光線反射率低落。 而且，藉由在反射層12(Mo/Si多層反射膜）與保護層 14(Ru保護層）之間形成中間層13，在形成保護層14時，亦 月b夠抑制]vio/Si多層反射膜的最上層亦即&層中的si擴散至 Ru保護層中。 在中間層13中氮的含有率小於〇.5at%時，上述進一步 抑制氧化的效果係有不充分的可能性，且抑制由Ru保護層 的氧化引起EUV光線反射率低落的效果係有不充分的可能 性。 詳細係如後述，在本發明，上述組成的中間層13係可 藉由在形成Mo/Si多層反射膜後，將Mo/Si多層反射膜的最 上層亦即Si層表面曝露在含氮氣體環境中來形成。但是， 推剛在中間層13的氮之含有率超過25at%的情況下，Mo/Si 多層反射膜的最上層亦即Si層成膜時，或是中間層13上所 11 201131615 形成之保護層14成膜時之任一情況，或是該等兩者成膜時 係被添加了氮，添加了氮之成膜，其在成膜中的缺點會增 加而有產生問題之可能性。亦即，在將保護層設為Ru時， 藉由將中間層設為如上述的組成，更能夠發揮效果。 從EUV光線反射率低落的觀點，中間層13係以含有0.5 〜15at%的氮且含有85〜99.5at%的Si為佳，以含有0.5〜 10at%的氮且含有80〜99.5at%的Si為較佳，以含有1〜9at% 的氮且含有91〜99at%的Si為又較佳，以含有3〜9at%的氮 且含有91〜97at%的Si為更佳，以含有5〜8at%的氮且含有 92〜95at%的Si為特佳。 因為中間層13中的Si有被侵蝕的可能性，所以中間層 13以不含有氟為佳。又，若中間層13中含有碳和氫，因為 有可能與該中間層13中的氧反應而將該中間層13中的氧排 出，致使該中間層13的構造劣化，所以該中間層13以不含 有碳和氫為佳。基於該等的理由，中間層13中氟、碳及氫 的含有率係各自以3at°/〇以下為佳，以lat%以下為更佳，以 0.05at%以下為特佳。又，同樣地，Ni、Y、Ti、La、Cr或 Rh之元素在中間層13的含有率，係該等元素的合計含有率 以3at%以下為佳，以lat%以下為更佳，以0.05at%以下為特 佳。 又，在中間層13中氧的含有率亦是以3at%以下為佳， 以lat%以下為更佳。 在本發明，中間層13的膜厚度為0.2〜2.5nm，就抑制 由Ru保護層的氧化引起EUV光線反射率低落之效果而言， 12 201131615 係以0.4〜2nm為較佳’以〇·5〜1.5nm為更佳。又，多層反 射膜的最上層的Si層之膜厚度，因為係曝露在含氮氣體環 境來形成中間層13 ’故以2〜4.8nm為佳，以2_5〜4.5nm為 更佳’以3.0〜4nm為特佳。 在本發明，上述組成的中間層13係可藉由形成Mo/Si 多層反射膜後，將該Mo/Si多層反射膜的最上層亦即si層表 面不曝露在大氣中而是曝露在含氮氣體環境中來使該&層 表面輕微地氮化，亦即藉由使Si層表面含有氮來形成。而 且’在本說明書所謂含氮氣體環境，係意味著氮氣環境或 是氮氣與氬氣等的惰性氣體之混合氣體環境。屬該混合氣 體環境時，環境中的氮氣濃度係以20v〇1%以上為佳，以 50vol%以上為較佳’以80v〇丨。/❶以上為更佳。 在此，形成Mo/Si多層反射膜後，將該Mo/Si多層反射 膜的最上層亦即Si層表面不曝露在大氣中而曝露在含氮氣 體環境中’係因為若在曝露在含氮氣體環境之前將^層表 面曝露在大氣中，該Si層表面會被氧化，即便之後曝露在 含I氣體環境’亦無法藉由該Si層表面的氮化來使該Si層表 面含有氮’而有無法形成含有氮及Si的中間層13之可能性。 在本發明’將Si層表面曝露之含氮氣體環境，係以氮 分歷（Torr)與曝露時間⑷的乘積為1 X 1〇-6T〇rr · s(-lL(Langmuir))以上為佳。將氮分壓以？3標記來表示時， 含氮氣體環境的氮分壓(Pa)與曝露時間（s)的乘積係以1 ·33χ lO^Pa · s以上為佳。 氣分壓與曝露時間的乘積係表示含氮氣體環境中的氮 13 201131615 與Si層表面碰撞的頻率之指標，以下，在本說明書，亦有 稱為「氮的曝露量」之情況。該值為1X1 〇_6Torr . s以上（1.33 xl(T4Pa· s以上），就藉由Si層表面的氮化來形成上述組成的 中間層13而言，以lxlO_3Torr . s以上（1.33χ10-1Ρα · s以上） 為較佳，以lxl(T2Torr · s以上（1.33Pa · s以上）為更佳，以1 父10-|丁〇〇>.8以上（13.3?&.5以上）為又更佳。又，氮分壓與 曝露時間的乘積係以lOOOTorr · s以下為佳。 又，在曝露Si層表面之含氮氣體環境的氮分壓，係以 1X1 (T4Torr 〜820Torr( 1 _33 X l(T2Pa 〜109.32kPa)為佳。 在此，含氮氣體環境為氮氣環境時，上述的氮分壓係 指該氮氣環境的環境氣體壓力。 為了防止Si層表面的氧化，在曝露Si層表面之含氮氣體 環境的氧濃度係以非常低為佳。具體上，在含氮氣體環境 中氮分壓為上述範圍時，亦即，在含氮氣體環境中氮分壓 為 lxl〇-4Torr〜820Torr(1.33xl(T2Pa〜109.32kPa)時，氣體 環境中的氧分壓係以1x 1 〇_6Torr( 1.33 X10_4Pa)以下為佳。 又，為了防止Si層表面的氧化，在將Si層表面曝露之含 氮氣體環境中，由含有〇3、H20及OH基的化合物所構成之 氣體成分的濃度亦以非常低為佳。具體上，在含氮氣體環 境之氮分壓為上述範圍時，亦即，在含氮氣體環境中氮分 壓為 1χ10·4Τοιτ〜820Torr(1.33xl0_2Pa〜109.32kPa)時，氣 體環境中之由含有〇3、H20及OH基的化合物所構成的氣體 成分之分壓係以分別為1X1 〇_6Torr( 1 _33 X1 (T4Pa)以下為佳。 又，因為有侵蝕Si層的可能性，在含氮氣體環境之f2 14 201131615 的濃度亦以非常低為佳。具體上’在含氮氣體環境之氣分 壓為上述範圍時’亦即，在含氮氣體環境之氮分壓為 1χ10·4τ〇π·〜820Torr(l_33xl(T2Pa〜l〇9.32kPa)時，氣體環境 中F2分壓係以lxHT6Torr(1.33><l(r4pa)以下為佳。 在本發明，將Si層表面曝露之含氮氣體環境的溫度係 以0〜170°C為佳。含氣氣體環境的溫度小於〇°c時，恐有因 真空中的殘留水分吸附造成影響的問題。含氮氣體環境的 溫度超過170°C時，Si層的氣化過度進行，有產生多 層反射膜的EUV光線反射率低落之可能性。 含氮氣體環境的溫度係以1〇〜160。(：為較佳，以2〇〜 150°C、20〜140°C、20〜120°C 為更佳。 而且’如後述’將Si層表面曝露在含氮氣體環境時， 亦可在上述溫度範圍將該Si層表面熱處理。 在本發明’藉由將Mo/Si多層反射膜的最上層亦即以層 表面曝露在含氮氣體環境中來形成中間層13，則保護層 14(Ru保護層）成膜後之EUV光線反射率不會降低，能夠提 升氧化耐久性，因此很適宜。 在後述的實施例1、2，將Si層表面曝露在含氮氣體環 境之時間係各自設為600sec、6000sec，但是將§丨層表面曝 露在含氮氣體環境之時間係不被此限定，可在滿足有關上 述含氮氣體環境的條件之範圍内適當地選擇。 而且’亦可以如實施例3、4的程序，在形成M〇/Si多層 反射膜後，將該Mo/Si多層反射膜的最上層亦即&層表面不 曝露在大氣中而是在曝露於含氮氣體環境時，II由在該含 15 201131615 氮氣體環境中進行熱處理來形成中間層13。將Mo/Si多層反 射膜的最上層亦即Si層表面曝露在含氮氣體環境時，藉由 熱處理該Si層表面，能夠促進該Si層表面氮化，亦即促進在 該Si層表面含有氮。 而且，在形成Mo/Si多層反射膜後，將該Mo/Si多層反 射膜的最上層不曝露在大氣中而是在含氮氣體環境中進行 熱處理方面，係可在形成Si層後，將形成有Mo/Si多層反射 膜之基板以保持在形成Si層後之成膜處理室内、或是以保 持在鄰接該成膜處理室之處理室内的狀態下，將處理室内 的氣體取代成為氮氣（或氮氣與氬氣等的惰氣之混合氣 體），在該取代後的氣體中進行熱處理Si層即可。 將Si層表面在含氮氣體環境中進行熱處理時之熱處理 溫度，係以120〜160°C為佳，以130〜150°C為特佳。 如實施例1〜4所示的程序般在減壓氣體環境下將S i層 表面曝露在氮氣之程序、或曝露在氮氣與氬氣等的惰氣之 混合氣體之程序，當多層反射膜的成膜、及保護層的成膜 係使用同一處理室來實施的情況下，若是將在實施將Si層 表面曝露在氮氣（或是氮氣與氬氣等的惰氣之混合氣體）的 程序後、且實施保護層的成膜之前將處理室内的氮氣（或氮 氣與氬氣等的惰氣之混合氣體)排氣這點列為重要考量，則 係較佳程序。又，該程序對於可藉由控制對Si層表面的氮 氣（或氮氣與氬氣等的惰氣之混合氣體）曝露量而來控制中 間層13的氮含量這點而言，亦是較佳程序。 又，如實施例3、4所示的程序，在形成Mo/Si多層反射 16 201131615 膜後，將該Mo/Si多層反射膜的最上層亦即Si層表面不曝露 在大氣中，而是在曝露於含氮氣體環境之際，藉由在該含 氮氣體環境中進行熱處理，可促進該Si層表面氮化亦即促 進在該Si層表面含有氮係已上述，而在減壓氣體環境下將 Si層表面曝露在氮氣、或氮氣與氬氣等的惰性氣體之混合 氣體的這種情況，就促進該Si層表面氮化亦即促進在該Si 層表面含有氮而言，將該減壓氣體環境保持在電漿狀態亦 是較佳。 但是，此時，若亦對在電漿狀態離子化的氮氣（或氮氣 與氬氣等的惰氣之混合氣體)施加電壓而對Si層表面進行離 子照射，則因為離子化的氮以被加速狀態碰撞Si層表面， Si層的氮化過度進行，而有產生Mo/Si多層反射膜的EUV光 線反射率低落之可能性，因此，就能夠適當的控制中間層 13的氮量這點而言，不對在電漿狀態離子化的氮氣（或氮氣 與氬氣等的惰氣之混合氣體)施加電壓、亦即不進行離子照 射乃是特佳。 又，在減壓氣體環境下將Si層表面曝露在氮氣、或氮 氣與氬氣等的惰性氣體之混合氣體時，就能夠促進Si層表 面的氮化亦即促進在Si層表面含有氮而言，在該減壓氣體 環境中對Si層表面照射紫外線乃是較佳。 在本發明，形成Mo/Si多層反射膜後，將該Mo/Si多層 反射膜的最上層亦即Si層表面，不曝露在大氣中，而是曝 露在含氮氣體環境時，在該含氮氣體環境下進行熱處理， 或是將該含氮氣體環境保持在電漿狀態，或是在該含氮氣 17 201131615 體環境中照射紫外線的情況下，該含氮氣體環境係以減壓 氣體環境為佳。該含氮氣體環境的壓力係以0.01〜〇.5mTorr 為佳，以0.1〜0.5mTorr為更佳。又，將含氮氣體環境保持 在電漿狀態、或是在含氮氣體環境中對Si層表面照射紫外 線時，該含氮氣體環境的溫度係以〇〜170°C為更佳。 保護層14係為了保護反射層12避免受到化學性、物理 性的侵蝕之目的而設置。EUVL用多層膜鏡係為了防止以下 情形而在反射層12上形成保護層：在製造EUVL用多層膜鏡 後所實施之使用臭氧水等的洗淨步驟引起反射層12的損 傷；在保持於真空之曝光機内為了提升生產性所實施的長 時間EUV光線照射引起反射層12的損傷；及為了除去EUVL 用多層膜鏡表面的碳污染而實施的洗淨引起反射層12的損 傷等。 因此，保護層14係從防止對反射層12的損傷之觀點來 選擇材料。 又，保護層14其本身亦以EUV光線反射率高為佳，如 此即便在形成保護層14後亦不會損害在反射層12的EUV光 線反射率。 在本發明’為了滿足上述條件，係形成RU層、或RU化 合物層荨作為保s隻層14。作為如此的Ru化合物，係例如選 自由RuB、RuNb及RuZr所組成群組之至少1種為佳。若保護 層14係Ru化合物層時，Ru的含有率係以5〇at%以上為佳、 80at%以上更佳、特別是90at%以上為佳。但是，保護層14 係RuNb層時’保護層14中的Nb含有率係以5〜4〇at%為佳， 18 201131615 以5〜30at%為更佳。 在本發明，保護層14表面的表面粗糙度rms係以〇 5nm 以下為佳。又，表面粗縫度rms為0.5nm以下係意味著二次 方平均平方根的表面粗糙度為〇.5nm以下。保護層14表面的 表面粗糙度大時，EUV光線反射率低落。 保護層14表面的表面粗糙度rms若為0.5nm以下，因為 能夠提高EUV光線反射率，乃是較佳。保護層14表面的表 面粗經度rms係以0.4nm以下為較佳，0.3nm以下為更佳。 保護層14的厚度係1〜10nm能夠提高EUV光線反射 率，乃是較佳。保護層14的厚度係以1〜5nm為較佳，以2 〜4nm為更佳。 保護層14可使用磁控管賤鍵法、離子射束機錢法等γ 所周知的成膜方法來成膜。 使用離子射束濺鍍法來形成Ru層作為保護層14時，係 使用Ru標靶作為標靶且使其在氬(Ar)氣體環境中放電即 "5J* 〇 具體上’係使用以下條件實施離子射束濺鍍法即可。 •濺鍍氣體：Ar氣（氣壓 i.3xl〇_2pa〜2.7xl〇-2paj •離子加速電壓：300〜1500V •成膜速度.〇.〇3〜0.30nm/sec 本發明的E U V L用多層膜鏡若係依照後述的實施例所 記載之程序進行臭氧水洗淨保護層14表面時，在洗淨前後 的EUV光線反射率低落係以0.9%以下為佳，以〇 5%以下為 更佳。 一 19 201131615 本發明的EUVL用多層膜鏡若係依照後述的實施例所 記載之程序而進行加熱處理時，在加熱處理前後的EUV光 線反射率低落係以7%以下為佳，以6%以下為更佳。 又’相較於臭氧水洗淨前述之EUV光線反射率低落， 在加熱處理前後之EUV光線反射率低落的值較大，係由於 為了確認本發明的效果，在後述的實施例使用了比製造 EUVL用多層膜鏡時所實施的加熱步驟更為嚴酷的條件來 實施加熱處理之緣故。 就使用本發明之EUVL用多層膜鏡之半導體積體電路 的製造方法進行說明，本發明係適用在藉由使用EUV光作 為曝光用光源的微影術法之半導體積體電路之製造方法。 具體上係在載物台上配置經塗布光阻之矽晶圓等的基板， 並在使用上述EUVL用多層膜鏡之反射型曝光裝置上設置 反射型光罩作為反射鏡。接著，將EUV光從光源透過反射 鏡而照射光罩，並藉由光罩使EUV光反射而照射在經塗布 光阻之基板。藉由該圖案轉印步驟，將電路圖案轉印至基 板上。經轉印電路圖案之基板係藉由顯像而將感光部分或 非感光部分蝕刻後，將光阻剝離。半導體積體電路係藉由 重複如此的步驟來製造。 實施例 以下，使用實施例來進一步說明本發明。 (貫施例1) 本實施例係製造如第1圖所表示的EUVL用多層膜鏡i。 作為成膜用的基板11 ’係使用Si〇2-Ti〇2系的玻璃基 201131615 板。該玻璃基板的熱膨脹係數為〇.2xl(T7/°C、楊格模數為 67GPa、泊松比（Poisson’s ratio)為 0.17 、比剛性為 3.07xl07m2/s2。藉由研磨該玻璃基板來形成表面粗糙度rms 為0.15nm以下的平滑表面。 在基板11的表面上係藉由使用離子射束濺鍍法將Mo 層及Si層交替地成膜重複50周期，來形成合計膜厚度為 340nm((2.3nm+4.5nm) X 50)的 Mo/Si 多層反射膜（反射層 12)。又，多層反射膜12的最上層為Si層。201131615 VI. Description of the Invention: [Technical Field of Invention] The present invention relates to a multilayer film mirror for EUV (EXTreme Ultraviolet) lithography used in semiconductor manufacturing and the like (hereinafter, This specification is referred to as "multilayer film mirror for EUVL" and a method of manufacturing the same. BACKGROUND OF THE INVENTION In the semiconductor industry, as a transfer technique for forming a fine pattern necessary for forming an integrated circuit composed of a fine pattern on a germanium substrate or the like, lithography using visible light and ultraviolet light has been used. Method. However, the miniaturization of semiconductor components is accelerating and is approaching the limits of previous lithography. In the case of the lithography method, the resolution limit of the pattern is about 1/2 of the exposure wavelength. Even if the immersion method is used, it is generally considered to be about 1/4 of the exposure wavelength, and even if an ArF laser (193 nm) immersion liquid is used. The legal system predicts that 45_ is the limit. Therefore, as an exposure technique using generations shorter than a short exposure wavelength of 45 nm, an exposure technique using an ultraviolet light of a shorter wavelength than an ArF laser, that is, an EUV lithography system, is considered to be promising. In the present specification, the term "EUV light" refers to a light having a wavelength of a soft X-ray region or a vacuum ultraviolet region, and specifically refers to a light having a wavelength of about 1 〇 to 2 〇 nm, particularly about 13 5 nm ± 〇 3 nm. Since the EUV light system is easily absorbed by all substances, and the refractive index of the substance at this wavelength is close to 1, it is impossible to use a refractive optical system such as lithography which previously used visible light or ultraviolet light. Therefore, EUV Photolithography 201131615 uses a reflective optics, a reflective reticle and mirror. The mirror used in EUV lithography has a structure in which a reflective layer that reflects EUV light is formed on a substrate made of glass or the like. As the reflective layer, since a high EUV light reflectance can be achieved, a multilayer reflective film in which a high refractive layer and a low refractive index layer are alternately laminated in plural times is usually used. Therefore, as a mirror used in EUV photolithography, a multilayer film mirror in which a multilayer reflective film is formed on such a substrate is generally used (see Patent Document 1). In order to protect the multilayer reflective film from chemical and physical insults, such a multilayer film mirror is mostly formed with a protective $ (protective cover layer) on the multilayer reflective film. In the case of the multilayer film mirror described in Patent Document 1, a protective cover layer comprising a material selected from the group consisting of ruthenium (Ru) and rhodium (Rh) and a compound or alloy selected from the above is provided. LIST OF INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In the multilayer reflective film of the multilayer film mirror for EUVL, a multilayer reflective film is generally used, and the Mo/Si multilayer is used. The reflective film is formed by using a molybdenum (Mo) layer as a low refractive index layer and a tantalum (Si) layer as a high refractive index layer. In the material of the protective layer of the multilayer film mirror for EUVL, it is preferable to use a high reflectance even when the surface of the protective layer is irradiated with EUV light, and it is preferable to use it. 4 201131615 However, when Ru is used as the material of the protective layer, in the steps (such as the washing step, heating step, etc.) performed in the manufacture of the multilayer mirror, or in the EUV exposure using EUV photolithography, The Ru protective layer and even the uppermost layer of the multilayer reflective film (the Si layer in the case of the Mo/Si multilayer reflective film) are oxidized, and there is a problem that the EUV light reflectance is lowered when the surface of the protective layer is irradiated with EUV light. In particular, since the EUV light reflectance at the time of EUV exposure is delayed, it is necessary to change the exposure conditions on the way, or it is necessary to replace the EUVL multilayer film mirror, and the life of the multilayer film mirror for EUVL is shortened. problem. Hereinafter, in the present specification, there are steps (for example, a washing step, a heating step, and the like) which are performed when manufacturing a multilayer mirror for EUVL, or when EUV exposure using Euv photolithography is performed, due to RU protection. The uppermost layer of the layer and even the multilayer reflective film is oxidized, so that the reflectance of the euv light when the surface of the protective layer is irradiated with EUV light is low, and is simply referred to as "the reflectance of the EUV light caused by the oxidation of the Ru protective layer is lowered". In view of the above circumstances, the present invention provides a multilayer film mirror for EUVL which suppresses the low reflectance of EUV light caused by oxidation of a Ru protective layer, and a method for producing the same. In order to solve the above problems, the inventors of the present invention have found that an intermediate layer containing a predetermined amount of nitrogen and Si is formed between the Mo/Si multilayer reflective film and the Ru protective layer. It is possible to suppress the low reflectance of the EUV light caused by the oxidation of the ru protective layer. 201131615 The present invention is based on the knowledge of the inventors of the present invention, and provides a multilayer film mirror for EUV lithography (multilayer film mirror for EUVL) which forms a reflective layer for reflecting EUV light on a substrate in order. And a multilayer film mirror for EUV lithography which is formed by protecting a protective layer of the reflective layer, wherein the reflective layer is a Mo/Si multilayer reflective film, and the protective layer is a Ru layer or a Ru compound layer, and An intermediate layer containing 0.5 to 25 at% of nitrogen and containing 75 to 99.5 at% of Si is formed between the reflective layer and the protective layer. The uppermost layer of the reflective layer composed of the Mo/Si multilayer reflective film is preferably a Si film, and the intermediate layer is preferably formed adjacent to the film. In the multilayer film mirror for EUVL of the present invention, the film thickness of the intermediate layer is preferably 0.2 to 2 nm. In the multilayer film mirror for EUVL of the present invention, the surface roughness rms of the surface of the protective layer is preferably 0.5 nm or less. In the multilayer film mirror for EUVL of the present invention, the film thickness of the protective layer is preferably 1 to 1 Onm. Moreover, the present invention provides a method of manufacturing a semiconductor integrated circuit, which is characterized in that a semiconductor integrated circuit is manufactured by exposing an exposed body using the multilayer film mirror for EUVL of the present invention. Further, the present invention provides a method for producing a multilayer film mirror for EUV lithography, which is formed by forming a multilayer reflection film on a film formation surface of a substrate after reflecting a multilayer reflection film of EUV light. a protective layer of a film to produce a multilayer film mirror for EUVL for EUV lithography (multilayer film for EuvL), characterized in that: 201131615, the multilayer reflective film is a Mo/Si multilayer reflective film, The protective layer is a Ru layer or a Ru compound layer, and after forming the Mo/Si multilayer reflective film, the surface of the uppermost layer of the Mo/Si multilayer reflective film, that is, the Si layer, is not exposed to the atmosphere but is exposed to a nitrogen-containing gas. The environment is such that the surface of the Si layer contains nitrogen to form the protective layer. In the method for producing a multilayer film mirror for EUVL of the present invention, the product of the nitrogen partial pressure (Torr) and the exposure time (s) of the nitrogen-containing gas atmosphere is lxl CT6 Torr.s (=1.33> < 10-4 Pa. s) = lL (Langmuir)) or more, and the temperature of the nitrogen-containing gas atmosphere is preferably 0 to 170 ° C. In the method for producing a multilayer film mirror for EUVL of the present invention, the product of the nitrogen partial pressure (Torr) and the exposure time (s) of the nitrogen-containing gas atmosphere is lxl -6 Torr.s or more and the nitrogen-containing gas environment A temperature of 0 to 160 ° C is preferred. In the method for producing a multilayer film mirror for EUVL of the present invention, the product of the nitrogen partial pressure (Torr) and the exposure time (s) of the nitrogen-containing gas atmosphere is 1×10 −6 Torr*s or more and the temperature of the nitrogen-containing gas environment is 0. ~150 ° C is better. In order to promote the nitrogen content on the surface of the Si layer, in the manufacturing method of the multilayer film mirror for EUVL of the present invention, when the surface of the Si layer is exposed to a nitrogen-containing atmosphere, the environment of the nitrogen-containing gas is maintained in the plasma. It is preferable to heat the surface of the Si layer or to irradiate the surface of the Si layer with ultraviolet rays. EFFECT OF THE INVENTION The multilayer film mirror for EUVL of the present invention can suppress the decrease in the reflectance of EUV light caused by the oxidation of the Ru protective layer. Moreover, the method of manufacturing 201131615 according to the present invention can manufacture a multilayer film mirror for EUVL which suppresses a decrease in reflectance caused by oxidation of the RU protective layer. Further, since the multilayer mirror for EUV lithography of the present invention can suppress the low reflectance of EUV light, it can be effectively utilized for manufacturing a semiconductor integrated circuit, and in particular, it is possible to manufacture a semiconductor integrated body having a fine pattern with good production efficiency. Circuit. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a multilayer film mirror for EUVL of the present invention. C. Embodiments J. Embodiments for carrying out the invention Hereinafter, the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an embodiment of a multilayer film mirror for EUVL of the present invention. The multilayer film mirror 1 for EUVL shown in Fig. 1 is formed by forming a reflective layer 12 for reflecting EUV light on the substrate 11 in order, and a protective layer 14 for protecting the reflective layer 12. However, the multilayer film mirror for EUVL of the present invention forms an intermediate layer 13 containing a predetermined amount of nitrogen and Si to be described later between the reflective layer 12 and the protective layer 14. The respective constituent elements of the multilayer film mirror 1 for EUVL will be described below. The substrate 11 satisfies the characteristics of a substrate for a multilayer film mirror for EUVL. Therefore, it is important that the substrate 11 has a low coefficient of thermal expansion. Specifically, the coefficient of thermal expansion of the substrate 11 is preferably 〇±1.〇Χ1〇-7Λ: preferably 〇±〇_3xl (T7/. (: is preferred, 〇±〇·2χΐ〇-7Α: More preferably, 〇±〇"><1〇-7/芄 is more preferably 0±0.05xl (r7/eC is particularly preferable. Further, the substrate is smooth, and multilayer for EUVL It is preferable that the cleaning liquid used for the cleaning of the film mirror is excellent in 201131615. As the substrate 11, specifically, a glass having a low thermal expansion coefficient, for example, Si〇2-Ti〇2 glass, etc., is used, but In this case, it is also possible to use a crystallized glass in which a quartz solid solution is precipitated, or a substrate such as quartz glass or tantalum or a metal, or a film such as a stress correction film may be formed on the substrate 11. The multilayer mirror can obtain a high reflectance, so that the substrate 11 has a smooth surface having a surface roughness rms of 0.15 nm or less. The size and thickness of the substrate 11 can be appropriately determined by the design value of the mirror or the like. It is preferable that the substrate 11 has no disadvantage on the surface on the side on which the multilayer reflective film 12 is formed. EUVL·reflection with a multilayer film mirror The required characteristic of 12 is the high EUV light reflectance. Specifically, when the light of the wavelength region of the EUV light is irradiated to the surface of the reflective layer 12 at an incident angle of 6 degrees, the maximum value of the light reflectance near the wavelength of 13.5 nm is 60%. The above is preferable, and it is more preferably 65% or more. Further, even when the intermediate layer 13 and the protective layer 14 are provided on the reflective layer 12, the maximum value of the light reflectance at a wavelength of 13.5 nm is 60% or more. Preferably, 65 ° / or more is more preferable. Since a high reflectance can be achieved in the EUV wavelength region, the reflective layer of the multilayer film mirror for EUVL is widely used to alternately use the high refractive index film and the low refractive index layer. A multilayer reflective film formed by laminating a plurality of layers. The multilayer film mirror for EUVL of the present invention uses a Mo/Si multilayer reflective film which is used as a low refractive index layer and a high refractive index. It is preferable that the Si layer of the layer is alternately laminated a plurality of times. 201131615 In the Mo/Si multilayer reflective film, the uppermost layer of the laminated M〇/Si multilayer reflective film is preferably formed as a Si film. When reflecting the film, the maximum EUV light reflectance is to be made. For the reflective layer 12' of 60% or more, the film thickness may be 2 3; the Mo layer of t〇lnm and the Si layer of the film thickness of 4.5±0.1 nm may be laminated in such a manner that the number of repeating units is 3〇 to 60. The respective layers constituting the Mo/Si multilayer reflection film may be formed by a known film formation method such as a magnetron sputtering method or an ion beam sputtering method to form a desired thickness. For example, using ions When the Mo/Si multilayer reflective film is formed by the beam smear method, the Mo target is used as the target system, and the Ar gas is used as the plating gas system (pressure l.3xl (r2pa~2.7xl0-2Pa), and the ion acceleration voltage is 300. ~1500V, film formation rate is 〇, 〇3 ～0.30nm/sec, and the Mo layer is formed into a film so as to have a thickness of 2.3 nm. Subsequently, a target is used as a target system, and an Ar gas is used as a sputtering gas system. (The air pressure is 1·3χΐ pa~2.7xi(r2pa) 'The ion acceleration voltage is 3〇〇~15〇〇v, the film formation speed is 0.03~0.30nm/sec, and the S1 layer is formed in such a manner that the thickness becomes seven. Film formation is preferred. This was taken as the i period, and the Mo/Si multilayer reflective film was formed by subjecting the M layer and the Si layer to 40 to 50 cycles. The multilayer film mirror for EUVL of the present invention has a gas containing 〇 5 to 25, such as %, and contains 75 to 99 5 〇/, between the reflective layer 12 and the protective layer 14. The intermediate layer 13' of the ^ suppresses the oxidation of the ^Ru protective layer causing the EUV light reflectance to be low. The reason why the intermediate layer 13' having the above-described composition is formed between the reflective layer 12 and the protective layer 能够 can suppress the decrease in the EUV light reflectance caused by the oxidation of the Ru protective layer is presumed as follows. 201131615 The intermediate layer 丨3 of the above composition is designed to prevent the oxidation of the S! ”Ru protective layer in the uppermost layer of the reflective layer 12 from containing a large amount of oxygen, thereby reducing the reflectance. The reflectance of the job has an effect of suppressing oxidation, thereby making it possible to perform the steps (for example, washing, defect inspection, heating step, lack of steps, etc.) performed in the manufacture of the EUVL multilayer film mirror, or When EUv exposure of EUV light microscopy occurs, a state in which the RU protective layer is oxidized is generated, and since the presence of the intermediate layer 13 having an oxidation inhibiting effect, the M〇/Sl layer reflection under the intermediate layer 13 can be suppressed. The film is oxidized, and more specifically, it is possible to suppress oxidation of the Si layer in the uppermost layer of the Mo/Si multilayer reflective film. As a result, it is presumed that the EUV light reflectance is lowered due to oxidation of the Ru protective layer. The intermediate layer 13 is formed between the reflective layer 12 (Mo/Si multilayer reflective film) and the protective layer 14 (Ru protective layer), and when the protective layer 14 is formed, the uppermost layer of the vio/Si multilayer reflective film is also suppressed. That is, the diffusion of si in the & layer In the Ru protective layer, when the content of nitrogen in the intermediate layer 13 is less than at5.5%, the above-described effect of further suppressing oxidation is insufficient, and the reflectance of EUV light caused by oxidation of the Ru protective layer is suppressed. The effect is insufficient. As will be described later, in the present invention, the intermediate layer 13 of the above composition can be formed by the uppermost layer of the Mo/Si multilayer reflective film after the Mo/Si multilayer reflective film is formed. The surface of the Si layer is formed by being exposed to a nitrogen-containing gas atmosphere. However, when the nitrogen content of the intermediate layer 13 is more than 25 at%, the uppermost layer of the Mo/Si multilayer reflective film, that is, the Si layer is formed, Or any of the cases in which the protective layer 14 formed on the intermediate layer 13 is formed by the formation of the film 11 201131615, or when the two films are formed, nitrogen is added, and a film of nitrogen is added, which is formed in the film. The disadvantage is increased, and there is a possibility that a problem arises. In other words, when the protective layer is made of Ru, the intermediate layer can be made to have the above-described composition, and the effect can be further exhibited. From the viewpoint of low EUV light reflectance, the middle Layer 13 is comprised of 0.5 to 15 at% of nitrogen and contains 85 to 99.5 at% of Si is preferable, and it is preferable to contain 0.5 to 10 at% of nitrogen and 80 to 99.5 at% of Si, and to contain 1 to 9 at% of nitrogen and contain 91 to 99 at% of Si. Preferably, Si containing 3 to 9 at% of nitrogen and containing 91 to 97 at% of Si is more preferable, and containing 5 to 8 at% of nitrogen and containing 92 to 95 at% of Si is particularly preferable because Si in the intermediate layer 13 has The possibility of being eroded, so the intermediate layer 13 is preferably free of fluorine. Further, if the intermediate layer 13 contains carbon and hydrogen, it is possible to react with oxygen in the intermediate layer 13 to oxygen in the intermediate layer 13. The discharge causes the structure of the intermediate layer 13 to deteriorate, so the intermediate layer 13 preferably contains no carbon or hydrogen. For the reason of the above, the content of fluorine, carbon and hydrogen in the intermediate layer 13 is preferably 3 at / / Torr or less, more preferably lat % or less, and particularly preferably 0.05 at % or less. In addition, the content ratio of the elements of Ni, Y, Ti, La, Cr, or Rh in the intermediate layer 13 is preferably 3 at% or less, and more preferably lat% or less. Below 0.05at% is particularly good. Further, the content of oxygen in the intermediate layer 13 is preferably 3 at% or less, more preferably lat% or less. In the present invention, the film thickness of the intermediate layer 13 is 0.2 to 2.5 nm, and in order to suppress the effect of lowering the reflectance of the EUV light caused by the oxidation of the Ru protective layer, 12 201131615 is preferably 0.4 to 2 nm. ~1.5nm is better. Further, the film thickness of the uppermost Si layer of the multilayer reflective film is preferably 2 to 4.8 nm, and more preferably 2 to 5 to 4.5 nm by 3.0 to be exposed to the atmosphere containing nitrogen gas. 4nm is especially good. In the present invention, the intermediate layer 13 of the above composition can be exposed to nitrogen without exposing the surface of the uppermost layer of the Mo/Si multilayer reflective film, that is, the si layer, by forming a Mo/Si multilayer reflective film. The surface of the & layer is slightly nitrided in a gaseous environment, that is, by containing nitrogen on the surface of the Si layer. Further, the term "nitrogen-containing gas atmosphere" as used herein means a nitrogen atmosphere or a mixed gas atmosphere of an inert gas such as nitrogen or argon. In the case of the mixed gas atmosphere, the nitrogen concentration in the environment is preferably 20 v 〇 1% or more, and more preferably 50 vol % or more. /❶ is better. Here, after the Mo/Si multilayer reflective film is formed, the uppermost layer of the Mo/Si multilayer reflective film, that is, the surface of the Si layer is not exposed to the atmosphere and exposed to the atmosphere containing nitrogen, because if it is exposed to nitrogen Before the gas environment, the surface of the layer is exposed to the atmosphere, and the surface of the Si layer is oxidized. Even after exposure to the atmosphere containing I, the surface of the Si layer cannot be nitrided by nitriding the surface of the Si layer. There is a possibility that the intermediate layer 13 containing nitrogen and Si cannot be formed. In the present invention, the nitrogen-containing atmosphere in which the surface of the Si layer is exposed is preferably a product of a nitrogen division (Torr) and an exposure time (4) of 1 X 1 〇 -6 T 〇 rr · s (-lL (Langmuir)) or more. . What is the partial pressure of nitrogen? When the 3 mark is used, the product of the partial pressure of nitrogen (Pa) and the exposure time (s) of the nitrogen-containing gas atmosphere is preferably 1.33 χ lO^Pa · s or more. The product of the partial pressure of gas and the exposure time indicates the index of the frequency of the collision of nitrogen in the nitrogen-containing atmosphere 13 201131615 with the surface of the Si layer. Hereinafter, this specification also refers to the case of "the amount of nitrogen exposure". The value is 1X1 〇_6 Torr. s or more (1.33 x 1 (T4Pa·s or more), and the intermediate layer 13 of the above composition is formed by nitridation of the surface of the Si layer, and is lxlO_3 Torr.s or more (1.33 χ 10-1 Ρ α) · s or more) is preferably lxl (T2 Torr · s or more (1.33 Pa · s or more) is more preferable, and 1 parent 10 -| 〇〇 〇〇 > .8 or more (13.3? & Further, the product of the nitrogen partial pressure and the exposure time is preferably 1000 Torr·s or less. Further, the partial pressure of nitrogen in the nitrogen-containing atmosphere exposed on the surface of the Si layer is 1×1 (T4 Torr to 820 Torr (1 _33). X l (T2Pa ~ 109.32 kPa) is preferred. Here, when the nitrogen-containing gas atmosphere is a nitrogen atmosphere, the above-mentioned nitrogen partial pressure refers to the ambient gas pressure of the nitrogen atmosphere. In order to prevent oxidation of the surface of the Si layer, the Si layer is exposed. The oxygen concentration in the nitrogen-containing atmosphere of the surface is preferably very low. Specifically, when the partial pressure of nitrogen in the nitrogen-containing atmosphere is in the above range, that is, the partial pressure of nitrogen in the atmosphere containing nitrogen is lxl 〇 -4 Torr. When the temperature is ~820 Torr (1.33xl (T2Pa~109.32kPa)), the partial pressure of oxygen in the gas environment is 1x 1 〇_6Torr ( 1.33 X10_4Pa). Further, in order to prevent oxidation of the surface of the Si layer, in a nitrogen-containing atmosphere in which the surface of the Si layer is exposed, the concentration of the gas component composed of the compound containing ruthenium 3, H20 and OH groups is also extremely low. Specifically, when the partial pressure of nitrogen in the nitrogen-containing atmosphere is in the above range, that is, in a nitrogen-containing atmosphere, the partial pressure of nitrogen is 1χ10·4Τοιτ~820 Torr (1.33×10 2 Pa to 109.32 kPa), in a gaseous environment. The partial pressure system of the gas component composed of the compound containing ruthenium 3, H20 and OH groups is preferably 1×1 〇_6 Torr (1 _33 X1 (T4Pa) or less. Further, since there is a possibility of eroding the Si layer, The concentration of f2 14 201131615 in a nitrogen-containing atmosphere is also very low. Specifically, when the partial pressure of gas in a nitrogen-containing atmosphere is within the above range, that is, the partial pressure of nitrogen in a nitrogen-containing atmosphere is 1χ10·4τ. When 〇π·~820 Torr (1_33xl (T2Pa~l〇9.32kPa)), the F2 partial pressure in the gas atmosphere is preferably lxHT6Torr (1.33><l(r4pa) or less. In the present invention, the surface of the Si layer is exposed. The temperature of the nitrogen-containing gas environment is preferably 0 to 170 ° C. In a gas-containing atmosphere When the temperature is less than 〇°c, there is a problem that the residual moisture in the vacuum is affected. When the temperature of the nitrogen-containing gas environment exceeds 170 ° C, the vaporization of the Si layer is excessively performed, and EUV light reflection of the multilayer reflection film is generated. The possibility of a low rate. The temperature of the nitrogen-containing gas environment is from 1 〇 to 160. (: Preferably, it is preferably 2 〇 to 150 ° C, 20 to 140 ° C, and 20 to 120 ° C. Further, as described later, when the surface of the Si layer is exposed to a nitrogen-containing atmosphere, The temperature range is to heat-treat the surface of the Si layer. In the present invention, the intermediate layer 13 is formed by exposing the uppermost layer of the Mo/Si multilayer reflective film, that is, the surface of the layer to a nitrogen-containing atmosphere, and the protective layer 14 (Ru protection) It is preferable that the EUV light reflectance after the film formation is not lowered, and the oxidation durability can be improved. In Examples 1 and 2 to be described later, the time for exposing the surface of the Si layer to the nitrogen-containing atmosphere is set to 600 sec. 6,000 sec, but the time when the surface of the 丨 layer is exposed to the nitrogen-containing gas environment is not limited thereto, and may be appropriately selected within the range satisfying the conditions of the nitrogen-containing gas environment. Moreover, 'may also be as in Example 3. The procedure of 4, after forming the M〇/Si multilayer reflective film, the uppermost layer of the Mo/Si multilayer reflective film, that is, the & layer surface is not exposed to the atmosphere but is exposed to the nitrogen-containing atmosphere, II Heat treatment in a nitrogen atmosphere containing 15 201131615 The intermediate layer 13 is formed. When the surface of the uppermost layer of the Mo/Si multilayer reflective film, that is, the surface of the Si layer, is exposed to a nitrogen-containing atmosphere, the surface of the Si layer can be nitrided by heat-treating the surface of the Si layer, that is, The surface of the Si layer contains nitrogen. Further, after the Mo/Si multilayer reflective film is formed, the uppermost layer of the Mo/Si multilayer reflective film is not exposed to the atmosphere but is heat treated in a nitrogen-containing atmosphere. After the Si layer is formed, the substrate on which the Mo/Si multilayer reflective film is formed is held in the film forming processing chamber after forming the Si layer, or in a state of being held in the processing chamber adjacent to the film forming processing chamber, the processing chamber is placed The gas is replaced by nitrogen (or a mixed gas of nitrogen and argon, etc.), and the Si layer may be heat-treated in the substituted gas. The heat treatment temperature of the surface of the Si layer in a nitrogen-containing atmosphere is heat-treated. Preferably, it is preferably 120 to 160 ° C, and is preferably 130 to 150 ° C. The procedure of exposing the surface of the Si layer to nitrogen under a reduced pressure atmosphere as in the procedures shown in Examples 1 to 4, or Exposed to inert gas such as nitrogen and argon In the case of mixing gas, when the film formation of the multilayer reflective film and the film formation of the protective layer are carried out using the same processing chamber, the surface of the Si layer is exposed to nitrogen gas (or nitrogen gas or argon gas, etc.). It is preferable to exhaust the nitrogen gas (or the mixed gas of inert gas such as nitrogen gas and argon gas) in the treatment chamber after the process of forming the gas mixture of the inert gas and before the film formation of the protective layer is considered as an important consideration. Further, the program is also capable of controlling the nitrogen content of the intermediate layer 13 by controlling the amount of nitrogen gas (or a mixed gas of inert gas such as nitrogen and argon) on the surface of the Si layer. Further, as in the procedures shown in Embodiments 3 and 4, after the Mo/Si multilayer reflection 16 201131615 film is formed, the uppermost layer of the Mo/Si multilayer reflection film, that is, the surface of the Si layer is not exposed to the atmosphere. Rather, when exposed to a nitrogen-containing gas environment, the surface of the Si layer is nitrided by heat treatment in the nitrogen-containing gas atmosphere, that is, the nitrogen layer is promoted on the surface of the Si layer. Exposing the surface of the Si layer in a gaseous environment In the case of a mixed gas of nitrogen or an inert gas such as nitrogen or argon, the surface of the Si layer is promoted to be nitrided, that is, the nitrogen gas is contained in the surface of the Si layer. The status is also preferred. However, at this time, if a voltage is applied to the surface of the Si layer by applying a voltage to nitrogen gas (or a mixed gas of inert gas such as nitrogen gas or argon gas) ionized in a plasma state, the ionized nitrogen is accelerated. The state collides with the surface of the Si layer, the nitridation of the Si layer is excessively performed, and there is a possibility that the EUV light reflectance of the Mo/Si multilayer reflection film is lowered, so that the amount of nitrogen of the intermediate layer 13 can be appropriately controlled. It is particularly preferable that no voltage is applied to the nitrogen gas ionized in the plasma state (or a mixed gas of inert gas such as nitrogen gas or argon gas), that is, ion irradiation is not performed. Further, when the surface of the Si layer is exposed to a mixed gas of nitrogen gas or an inert gas such as nitrogen gas or argon gas in a reduced-pressure atmosphere, the surface of the Si layer can be promoted to be nitrided, that is, it is promoted to contain nitrogen on the surface of the Si layer. It is preferable to irradiate the surface of the Si layer with ultraviolet rays in the atmosphere of the reduced pressure gas. In the present invention, after the Mo/Si multilayer reflective film is formed, the uppermost layer of the Mo/Si multilayer reflective film, that is, the surface of the Si layer, is not exposed to the atmosphere, but is exposed to the nitrogen-containing atmosphere, and the nitrogen is contained therein. When the heat treatment is carried out in a gaseous environment, or the nitrogen-containing gas environment is maintained in a plasma state, or in the case where the nitrogen gas is irradiated in a nitrogen atmosphere, the nitrogen-containing gas environment is preferably a reduced-pressure gas atmosphere. . The pressure in the nitrogen-containing gas atmosphere is preferably 0.01 to 0.5 mTorr, more preferably 0.1 to 0.5 mTorr. Further, when the nitrogen-containing gas atmosphere is maintained in a plasma state or the surface of the Si layer is irradiated with ultraviolet rays in a nitrogen-containing gas atmosphere, the temperature of the nitrogen-containing gas atmosphere is preferably 〇 170 ° C. The protective layer 14 is provided for the purpose of protecting the reflective layer 12 from chemical and physical attack. The EUVL multilayer film mirror system forms a protective layer on the reflective layer 12 in order to prevent the damage of the reflective layer 12 caused by the cleaning step using ozone water or the like after the multilayer mirror for EUVL is manufactured; In the exposure machine, damage of the reflective layer 12 is caused by long-time EUV light irradiation for improving productivity, and damage by the cleaning of the reflective layer 12 is performed in order to remove carbon contamination on the surface of the multilayer film mirror for EUVL. Therefore, the protective layer 14 selects a material from the viewpoint of preventing damage to the reflective layer 12. Further, the protective layer 14 itself preferably has a high EUV light reflectance, so that the EUV light reflectance at the reflective layer 12 is not impaired even after the protective layer 14 is formed. In the present invention, in order to satisfy the above conditions, an RU layer or a RU compound layer is formed as the s-only layer 14. As such a Ru compound, for example, at least one selected from the group consisting of RuB, RuNb and RuZr is preferable. When the protective layer 14 is a Ru compound layer, the content of Ru is preferably 5 〇 at% or more, more preferably 80 at% or more, and particularly preferably 90 at% or more. However, when the protective layer 14 is a RuNb layer, the Nb content in the protective layer 14 is preferably 5 to 4 〇 at%, and 18 201131615 is more preferably 5 to 30 at%. In the present invention, the surface roughness rms of the surface of the protective layer 14 is preferably 〇 5 nm or less. Further, the surface roughness rms of 0.5 nm or less means that the surface roughness of the square root mean square is 〇.5 nm or less. When the surface roughness of the surface of the protective layer 14 is large, the EUV light reflectance is low. When the surface roughness rms of the surface of the protective layer 14 is 0.5 nm or less, it is preferable because the EUV light reflectance can be improved. The surface roughness rms of the surface of the protective layer 14 is preferably 0.4 nm or less, more preferably 0.3 nm or less. It is preferable that the thickness of the protective layer 14 is 1 to 10 nm to improve the EUV light reflectance. The thickness of the protective layer 14 is preferably 1 to 5 nm, more preferably 2 to 4 nm. The protective layer 14 can be formed by a film forming method known by γ such as a magnetron 贱 bond method or an ion beam ray method. When the Ru layer is formed as the protective layer 14 by ion beam sputtering, the Ru target is used as a target and is discharged in an argon (Ar) gas atmosphere, that is, "5J* 〇 specifically" uses the following conditions The ion beam sputtering method can be carried out. • Sputtering gas: Ar gas (air pressure i.3xl〇_2pa~2.7xl〇-2paj • Ion accelerating voltage: 300~1500V • Film forming speed. 〇.〇3~0.30nm/sec Multilayer film for EUVL of the present invention When the surface of the protective layer of ozone water is washed according to the procedure described in the examples below, the reflectance of the EUV light before and after the cleaning is preferably 0.9% or less, more preferably 5% or less. 19 201131615 When the multilayer film mirror for EUVL of the present invention is subjected to heat treatment in accordance with the procedure described in the examples to be described later, the EUV light reflectance before and after the heat treatment is preferably 7% or less, and preferably 6% or less. Further, in view of the fact that the EUV light reflectance is lowered as compared with the ozone water, the value of the EUV light reflectance before and after the heat treatment is large, and the effect of the present invention is determined in order to confirm the effect of the present invention. The heat treatment is carried out under conditions that are more severe than the heating step performed when manufacturing the multilayer film mirror for EUVL. The method for producing a semiconductor integrated circuit using the multilayer film mirror for EUVL of the present invention will be described. A method of manufacturing a semiconductor integrated circuit using a lithography method using EUV light as a light source for exposure. Specifically, a substrate on which a photoresist such as a photoresist is applied is placed on a stage, and the above-described substrate is used. In the EUVL, a reflective reticle is provided as a mirror on the reflective exposure apparatus of the multilayer lenticular mirror. Then, the EUV light is transmitted from the light source through the mirror to the reticle, and the EUV light is reflected by the reticle to be irradiated on the coated light. The substrate is transferred to the substrate by the pattern transfer step. The substrate of the transfer circuit pattern is etched by the photosensitive portion or the non-photosensitive portion by development, and the photoresist is stripped. The integrated circuit is manufactured by repeating such steps. EXAMPLES Hereinafter, the present invention will be further described by way of examples. (Example 1) This example is a multilayer film mirror for EUVL shown in Fig. 1 As the substrate 11 for film formation, a glass-based 201131615 plate of Si〇2-Ti〇2 type was used. The coefficient of thermal expansion of the glass substrate was 〇.2xl (T7/°C, Young's modulus was 67 GPa, Poisson's ratio ( Poisson's ratio) The glass substrate is ground to form a smooth surface having a surface roughness rms of 0.15 nm or less by 0.17 and a specific rigidity of 10.5 nm or less. On the surface of the substrate 11, a Mo layer is formed by ion beam sputtering. And the Si layer was alternately formed into a film for 50 cycles to form a Mo/Si multilayer reflection film (reflection layer 12) having a total film thickness of 340 nm ((2.3 nm + 4.5 nm) X 50). Further, the multilayer reflection film 12 was the most The upper layer is the Si layer.
Mo層及Si層的成膜條件係如以下。 (Mo層的成膜條件） •標靶：Mo標靶 •濺鍍氣體：Ar氣（氣體壓0.02Pa) •電壓：700V •成膜速度：〇.〇64nm/sec •膜厚度：2.3nm (Si層的成膜條件） •標靶：Si標靶(摻雜硼） •濺鍍氣體：Ar氣（氣體壓0.02Pa) •電壓：700V •成膜速度：〇.〇77nm/sec •膜厚度：4.5nm 隨後，將Mo/Si多層反射膜的最上層的Si層表面按照下 述條件而曝露在含氮氣體環境。 (曝露條件） 21 201131615 •载氣：Ar氣、流量I7sccm •曝露氣體：氮氣、流量50sccm (在RF放電中供給氮氣及載氣） •氮氣分壓：0.2mTorr(2.6xl0_2Pa) •氣體環境壓力：〇.3mTorr(3.5Torrxl(T2Pa) •氣體環境溫度：2(TC •曝露時間：600sec •曝露量：1.2xl〇5L(lL(Langmuir)=lxl(T6T〇n·. s=1.33 xl〇'4Pa . s)The film formation conditions of the Mo layer and the Si layer are as follows. (Formation conditions of Mo layer) • Target: Mo target • Sputter gas: Ar gas (gas pressure 0.02 Pa) • Voltage: 700 V • Film formation speed: 〇.〇64 nm/sec • Film thickness: 2.3 nm ( Film formation conditions of the Si layer) • Target: Si target (doped with boron) • Sputter gas: Ar gas (gas pressure 0.02 Pa) • Voltage: 700 V • Film formation speed: 〇.〇77 nm/sec • Film thickness : 4.5 nm Subsequently, the surface of the uppermost Si layer of the Mo/Si multilayer reflective film was exposed to a nitrogen-containing gas atmosphere under the following conditions. (Exposure conditions) 21 201131615 • Carrier gas: Ar gas, flow rate I7sccm • Exposure gas: nitrogen, flow rate 50sccm (supply nitrogen and carrier gas in RF discharge) • Nitrogen partial pressure: 0.2mTorr (2.6xl0_2Pa) • Gas ambient pressure: 3.3mTorr (3.5 Torrxl (T2Pa) • Gas ambient temperature: 2 (TC • Exposure time: 600 sec • Exposure: 1.2×l 〇 5 L (lL (Langmuir) = lxl (T6T〇n·. s=1.33 xl〇'4Pa) .s)
•RF放電的頻率：ι.8ΜΗζ • RF能量：500W 隨後’使用離子射束濺鍍法形成保護層14亦即Ru層。 保護層14的形成條件係如以下。 •標靶：Ru標靶 •濺鍍氣體：Ar氣（氣體壓〇.〇2Pa)• Frequency of RF discharge: ι.8 ΜΗζ • RF energy: 500 W Subsequently, a protective layer 14, that is, a Ru layer, was formed by ion beam sputtering. The formation conditions of the protective layer 14 are as follows. • Target: Ru target • Sputter gas: Ar gas (gas pressure 〇.〇2Pa)
•電壓：700V •成膜速度.0.052nm/sec •膜厚度：2.5nm 對按照上述程序所得到的EUvl用多層膜鏡，實施下述 的評價。 (1)膜組成 藉由使用X射線光電子分光裝置(X_ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（M〇/Si多層反射膜）12之深度方向組 22 201131615 成，確認係在Mo/Si多層反射膜的最上層亦即&層與保護層 14之間形成有中間層13。中間層13的組成係氮6at%、 Si94at%。又’中間層13的膜厚度為inm。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗糖度rms為0.15nm。 (3) 财洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。在 該處理的前後對保護層14表面照射EUV光（波長I3.5nm)，且 使用EUV反射率計測定Euv反射率。在該處理的前後之 EUV反射率的降低為〇.5〇/0。 (4) 而彳加熱處理性 對EUVL用多層膜鏡，在21〇t進行加熱處理（大氣 中）1〇分鐘。該處理前後的EUV反射率降低係4.1〇/。。 (實施例2) 實施例2係除了將在含氮氣體環境的曝光條件設為以 下條件之外，係按照與實施例丨同樣的程序實施。 (曝露條件） •載氣：Ar氣、流量i7sccm •曝露氣體：氮氣、流量50scc.m (在RF放電中供給氮氣及載氣） •氮氣分壓：0.2mTorr(2.6xl(y2Pa) 23 201131615 •氣體環境壓力：0.3mTorr(3.5Torrxl(T2Pa) •氣體環境溫度：20°C •曝露時間：6000sec •曝露量：1.2xl06L(lL(Langmuir)=lxl(T6Torr· s=1.33 xlO'4Pa · s) • RF放電的頻率：1.8MHz• Voltage: 700 V • Film formation rate: 0.052 nm/sec • Film thickness: 2.5 nm The following evaluation was carried out for the EUvl multilayer film mirror obtained according to the above procedure. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer (M〇/Si multilayer reflective film) 12 by using an X-ray photoelectron spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). The depth direction group 22 201131615 was confirmed to have an intermediate layer 13 formed between the upper layer of the Mo/Si multilayer reflective film, that is, the & layer and the protective layer 14. The composition of the intermediate layer 13 is 6 at% of nitrogen and Si94 at%. Further, the film thickness of the intermediate layer 13 is inm. (2) Surface roughness The surface roughness of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments Co., Ltd.: number SPI3800). The surface roughness rms of the protective layer 14 was 0.15 nm. (3) Purity of the cleaning The surface of the protective layer 14 is rotated and washed for 6 seconds using ozone water. The surface of the protective layer 14 was irradiated with EUV light (wavelength I3.5 nm) before and after the treatment, and the Euv reflectance was measured using an EUV reflectometer. The decrease in EUV reflectance before and after the treatment was 〇.5 〇/0. (4) 彳 Heat treatment property The multilayer film mirror for EUVL was heat-treated (atmosphere) at 21 Torr for 1 Torr. The EUV reflectance reduction before and after this treatment was 4.1 〇/. . (Example 2) Example 2 was carried out in the same manner as in Example 之外 except that the exposure conditions in a nitrogen-containing gas atmosphere were set to the following conditions. (Exposure conditions) • Carrier gas: Ar gas, flow rate i7sccm • Exposure gas: Nitrogen, flow rate 50scc.m (supply nitrogen and carrier gas in RF discharge) • Nitrogen partial pressure: 0.2mTorr (2.6xl (y2Pa) 23 201131615 • Gas ambient pressure: 0.3mTorr (3.5Torrxl (T2Pa) • Gas ambient temperature: 20°C • Exposure time: 6000sec • Exposure: 1.2xl06L (lL(Langmuir)=lxl(T6Torr· s=1.33 xlO'4Pa · s) • Frequency of RF discharge: 1.8MHz
• RF能量：500W 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置(X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，確認係在Mo/Si多層反射膜的最上層亦即Si層與保護層 14之間形成有中間層13。中間層13的組成係氮8at%、 Si92at%。又，中間層13的膜厚度為lnm。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗縫度rms為0.15nm。 (3) 耐洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。在 該處理的刖後對保遵層14表面照射EUV光（波長13 5nm)，且 24 201131615 使用EUV反射率計測定EUV反射率。在該處理的前後之 EUV反射率的降低為〇3%。 (4)而ί加熱處理性 對EUVL用多層膜鏡，在210°C進行加熱處理（大氣 中）10分鐘。該處理前後的EUV反射率降低係3 7%。 (實施例3) 實施例3係除了使用以下的曝露條件（無RF放電）實施 熱處理來代替Si層表面曝露在含氮氣體環境（氮氣與氬氣的 混合氣體）以外’係按照與實施例1同樣的程序實施。• RF energy: 500 W The following evaluation was carried out for the EUVL multilayer film obtained according to the above procedure. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction composition, it was confirmed that the intermediate layer 13 was formed between the Si layer and the protective layer 14 which is the uppermost layer of the Mo/Si multilayer reflective film. The composition of the intermediate layer 13 is 8 at% of nitrogen and Si92 at%. Further, the film thickness of the intermediate layer 13 was 1 nm. (2) Surface roughness The surface roughness of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments Co., Ltd.: number SPI3800). The surface of the protective layer 14 has a rough rms of 0.15 nm. (3) Washing resistance The surface of the protective layer 14 was spin-washed using ozone water for 6 seconds. After the treatment, the surface of the layer 14 was irradiated with EUV light (wavelength 13 5 nm), and 24 201131615 EUV reflectance was measured using an EUV reflectometer. The decrease in EUV reflectance before and after the treatment was 〇3%. (4) ί Heat treatment property The multilayer film mirror for EUVL was heat-treated (atmosphere) at 210 ° C for 10 minutes. The EUV reflectance reduction before and after this treatment was 3 7%. (Example 3) Example 3 was carried out except that the surface of the Si layer was exposed to a nitrogen-containing gas atmosphere (a mixed gas of nitrogen gas and argon gas) in addition to the following exposure conditions (without RF discharge). The same procedure is implemented.
Mo/Si多層反射膜形成後，不曝露在大氣中，而是將 Mo/Si多層反射膜的最上層之^層表面按照下述條件在含 氮氣體環境中（氮氣與氬氣的混合氣體中）進行熱處理。 (曝露條件） •環境氣體：Ar氣（載氣）、流量17sccm。氮氣、流量 50sccm •氮氣分壓：0.2mTorr(2.6xlCT2Pa) •氣體環境壓力：0.3mTorr(3.5xl(T2Pa) •熱處理溫度：140°C •熱處理時間：600sec •氮分壓X熱處理時間（在含氮氣體環境之曝露時間）： 1.2xl〇5L(lL(Langmuir)=lxlO'6Torr · s=l.33xlO'4Pa · s) 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1)膜組成 25 201131615 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，確認係在Mo/Si多層反射膜的最上層亦即Si層與保護層 14之間形成有中間層13。中間層13的組成係氮6at%、 Si94at%。又，中間層13的膜厚度為lnm。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗縫度rms為0.15nm。 (3) 财洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。在 該處理的前後對保護層14表面照射EUV光（波長13 5nm)，且 使用EUV反射率計(AIXUV公司製MBR(製品名）)測定EUV 反射率。在該處理的前後之EUV反射率的降低為〇 5〇/〇。 (4) 耐加熱處理性 對EUVL用多層膜鏡，在21(rc進行加熱處理（大氣 中）ιο分鐘。該處理前後的Euv反射率降低係4 3〇/。。 (實施例4) 實施例4係除了將在含氮氣體環境中（氮氣與氬氣的混 合氣體中）的熱處理條件設為以下條件之外，係實施與實施 例3同樣的程序。 (熱處理條件） 26 201131615 •環境氣體：Ar氣（載氣）、流量17sccm。氮氣、流量 50sccm •氮氣分壓：〇.2mTorr(2.6xl(T2Pa) •氣體環境壓力：〇.3mTorr(3.5xl(T2Pa) •熱處理溫度：140°C •熱處理時間：6000sec •氮分壓X熱處理時間（在含氮氣體環境之曝露時間）： 1.2xl06L(lL(Langmuir)=lxl0'6Torr · s=1.33xlO'4Pa · s) 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成’確認係在Mo/Si多層反射膜的最上層亦即Si層與保護層 14之間形成有中間層13。中間層13的組成係氮8at0/〇、 Si92at%。又’中間層13的膜厚度為lnm。 (2) 表面粗錄度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確s忍保濩層14的表面粗縫度。保護層14的表面 粗链度rms為0.15nm。 (3) 财洗淨性 使用臭乳水將保瘦層14表面旋轉洗淨處理計6〇〇秒。在 27 201131615 忒處理的前後對保護層14表面照射EUV光（波長13.5nm)，且After the Mo/Si multilayer reflective film is formed, it is not exposed to the atmosphere, but the surface of the uppermost layer of the Mo/Si multilayer reflective film is in a nitrogen-containing atmosphere (mixed gas of nitrogen and argon) according to the following conditions. ) heat treatment. (Exposure conditions) • Ambient gas: Ar gas (carrier gas), flow rate 17sccm. Nitrogen, flow rate 50sccm • Nitrogen partial pressure: 0.2mTorr (2.6xlCT2Pa) • Gas ambient pressure: 0.3mTorr (3.5xl (T2Pa) • Heat treatment temperature: 140°C • Heat treatment time: 600sec • Nitrogen partial pressure X heat treatment time (inclusive) Exposure time in a nitrogen atmosphere: 1.2xl〇5L (lL(Langmuir)=lxlO'6Torr · s=l.33xlO'4Pa · s) The following evaluation was performed on the multilayer film mirror for EUVL obtained according to the above procedure. (1) Membrane composition 25 201131615 The surface from the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) was measured by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction of 12, it was confirmed that the intermediate layer 13 was formed between the Si layer and the protective layer 14 which is the uppermost layer of the Mo/Si multilayer reflective film. The composition of the intermediate layer 13 was 6 at% and Si94 at%. The film thickness of the intermediate layer 13 was 1 nm. (2) Surface roughness The surface of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments: number SPI3800). Roughness. Surface of protective layer 14 The slit rms is 0.15 nm. (3) Purity The surface of the protective layer 14 is rotated and washed for 6 seconds using ozone water. The surface of the protective layer 14 is irradiated with EUV light (wavelength 13 5 nm) before and after the treatment. The EUV reflectance was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV Co., Ltd.). The EUV reflectance reduction before and after the treatment was 〇5 〇 / 〇. (4) Heat treatment resistance for EUVL Multilayer film mirror, heat treatment (atmosphere) for 21 minutes at rc. The Euv reflectance reduction before and after the treatment was 4 3 〇 / (Example 4) Example 4 except that it will be in a nitrogen-containing atmosphere. The heat treatment conditions (in the mixed gas of nitrogen gas and argon gas) were the same as those in the following Example 3. (Heat treatment conditions) 26 201131615 • Ambient gas: Ar gas (carrier gas), flow rate: 17 sccm. Nitrogen, flow rate 50sccm • Nitrogen partial pressure: 〇.2mTorr (2.6xl (T2Pa) • Gas ambient pressure: 〇.3mTorr (3.5xl (T2Pa) • Heat treatment temperature: 140°C • Heat treatment time: 6000sec • Nitrogen partial pressure X heat treatment Time (exposure time in a nitrogen-containing environment): 1.2x L06L (lL (Langmuir) = lxl0'6 Torr · s = 1.33xlO'4Pa · s) The following evaluation was carried out on the multilayer film mirror for EUVL obtained by the above procedure. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). The depth direction composition 'confirmed that the intermediate layer 13 is formed between the Si layer and the protective layer 14 at the uppermost layer of the Mo/Si multilayer reflective film. The composition of the intermediate layer 13 is nitrogen 8 at 0 / 〇, Si 92 at %. Further, the film thickness of the intermediate layer 13 was 1 nm. (2) Surface roughness The surface roughness of the ruthenium layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (Seiko Instruments Co., Ltd.: number SPI3800). The surface of the protective layer 14 has a thick chain rms of 0.15 nm. (3) Purity of the cleansing The surface of the thin layer 14 is rotated and washed for 6 seconds using the stinky water. The surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm) before and after the treatment of 27 201131615, and
使用EUV反射率計（AIXUV公司製MBR(製品名）)測定EUV 反射率。在該處理的前後之EUV反射率的降低為0 3〇/〇。 (4)耐加熱處理性 對EUVL用多層膜鏡，在210°c進行加熱處理（大氣 中）1〇分鐘。該處理前後的Ευν反射率降低係3.7%。 (比較例1) 比較例1係除了形成反射層（Mo/Si多層反射膜）12後，不 將Mo/Si多層反射膜的最上層亦即si層曝露在含氮氣體環 境而形成保護層14以外，係與實施例1實施同樣的程序。 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，無法確認在Mo/Si多層反射膜的最上層亦即Si層與保護 層14之間形成有中間層13，而在Si層與保護層14的積層體 之氮含有率為0%。 (2) 表面粗链度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗链度rms為0.15nm。 28 201131615 (3) 而ί洗淨性 使用臭氣水將保護層14表面旋轉洗淨處理計600秒。在 °亥處理的則後對保護層14表面照射E U V光（波長13.5 n m )，且 使用EUV反射率計測定反射率。在該處理的前後之 EUV反射率的降低為2.1%。 從垓結果，確認相較於實施例1〜4的euvl用多層膜 鏡’比較例1的EUVL用多層膜鏡係耐洗淨性差。 (4) 耐加熱處理性 對BUVL用多層膜鏡’在21〇。〇進行加熱處理（大氣 中）1〇分鐘。該處理前後的EUV反射率降低係7 8%。 從該結果，確認相較於實施例1〜4的EUVL用多層 鏡，比較例1的EUVL用多層膜鏡係耐加熱處理性差。 、 (比較例2) 露 比較例2係除了將Si層表面依下述曝露條件曝 氣體環境來取代含氮氣體環境以外，係使用與實施众 的程序實施。 ’ (曝露條件） 流量17sccm(在RF放電中供 '、给 Ar •暴露氣體：Ar氣、 氣）The EUV reflectance was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV Co., Ltd.). The decrease in EUV reflectance before and after the treatment was 0 3 〇/〇. (4) Heat treatment resistance The multilayer film mirror for EUVL was heat-treated (atmosphere) at 210 ° C for 1 minute. The Ευν reflectance reduction before and after the treatment was 3.7%. (Comparative Example 1) In Comparative Example 1, the protective layer 14 was formed by exposing the Si layer, which is the uppermost layer of the Mo/Si multilayer reflective film, to the atmosphere containing nitrogen, except that the reflective layer (Mo/Si multilayer reflective film) 12 was formed. The same procedure as in the first embodiment was carried out. The following evaluation was carried out on the multilayer film mirror for EUVL obtained in accordance with the above procedure. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction composition, it was not confirmed that the intermediate layer 13 was formed between the Si layer and the protective layer 14 in the uppermost layer of the Mo/Si multilayer reflective film, and the nitrogen content of the laminated body of the Si layer and the protective layer 14 was 0. %. (2) Surface roughness The surface roughness of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments Co., Ltd.: number SPI3800). The surface of the protective layer 14 has a thick chain rms of 0.15 nm. 28 201131615 (3) And ί Washability The surface of the protective layer 14 was rotated and washed for 600 seconds using odorous water. After the treatment at ° hai, the surface of the protective layer 14 was irradiated with E U V light (wavelength 13.5 n m ), and the reflectance was measured using an EUV reflectometer. The EUV reflectance reduction before and after the treatment was 2.1%. From the results of the enthalpy, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 1 was inferior in washability as compared with the multilayer film for euvl of Examples 1 to 4. (4) Resistance to heat treatment The multilayer film mirror for BUVL was at 21 〇. 〇 Heat treatment (atmosphere) for 1 minute. The EUV reflectance reduction before and after this treatment was 7 8%. From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 1 was inferior in heat treatment resistance compared to the multilayer mirror for EUVL of Examples 1 to 4. (Comparative Example 2) The comparative example 2 was carried out by using a program in which the surface of the Si layer was exposed to a gas atmosphere in accordance with the following exposure conditions instead of the nitrogen-containing gas atmosphere. ' (Exposure conditions) Flow rate 17sccm (for 'in the RF discharge', give Ar • Exposure gas: Ar gas, gas)
•氣體環境壓力：〇.lmTorr(1.3xlO_2Pa) •氣體環境溫度：20°C •曝露時間：600sec • RF放電的頻率：1.8MHz• Gas ambient pressure: 〇.lmTorr (1.3xlO_2Pa) • Gas ambient temperature: 20°C • Exposure time: 600sec • Frequency of RF discharge: 1.8MHz
• RF能量：500W 29 201131615 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，無法確認在Mo/Si多層反射膜的最上層亦即Si層與保護 層14之間形成有中間層13，而在Si層與保護層14的積層體 中氮含有率為0%。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗縫度rms為0.15nm。 (3) 耐洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計600秒。在 該處理的前後對保護層14表面照射EUV光(波長I3.5nm)，且 使用EUV反射率計測定EUV反射率。在該處理的前後之 EUV反射率的降低為2.9%。 從該結果，確認相較於實施例1〜4的EUVL用多層膜 鏡，比較例2的EUVL用多層膜鏡係耐洗淨性差。 (4) 耐加熱處理性 對EUVL用多層膜鏡，在210°C進行加熱處理（大氣 中）10分鐘。該處理前後的EUV反射率降低係7.8%。 30 201131615 從該結果，確認相較於實施例丨〜4的EUVL用多層膜 鏡，比較例2的EUVL用多層膜鏡係耐加熱處理性差。 (比較例3) 比較例3係除了未將Si層表面進行熱處理且亦未進行 RF放電，而使用下述曝露條件實施曝露以外，係使用與實 施例1同樣的程序實施。 形成Mo/Si多層反射膜後，不曝露在大氣中，而是將 Mo/Si多層反射膜的最上層之Si層表面，按照下述條件在含 氮氣體環境中（氮氣與氬氣的混合氣體環境中）曝露。 (曝露條件） •環境氣體：Ar氣（載氣）、流量17sccm。氮氣、流量 50sccm •氮氣分壓：〇.2mTorr(2_6xl(T2Pa) •氣體環境壓力：〇.3mTorr(3.5xlO_2Pa) •熱處理溫度：20°C •熱處理時間：600sec 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1)膜組成 藉由使用X射線光電子分光裝置（x-ray photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，無法確認在Mo/Si多層反射膜的最上層亦即以層與保護 層14之間形成有中間層13，而在Si層與保護層14的積層體 31 201131615 之氮含有率為ο.2%。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗糙度rms為0_15nm。 (3) 耐洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。& 該處理的前後對保護層14表面照射EUV光（波長π.5nm)，且 使用EUV反射率計(AIXUV公司製MBR(製品名）)測定Euv 反射率。在該處理的前後之EUV反射率的降低為丨.9%。從 該結果，確認相較於實施例1〜4的EUVL用多層膜鏡，比較 例3的EUVL用多層膜鏡係对洗淨性差。 (4) 而ί加熱處理性 對EUVL用多層膜鏡，在210°C進行加熱處理（大氣 中）1〇分鐘。該處理前後的EUV反射率降低係7.4%。 從該結果，確認相較於實施例1〜4的EUVL用多廣膜 鏡，比較例3的EUVL用多層膜鏡係耐加熱處理性差。 (比較例4) 比較例4係除了按照下述條件在A r氣體環境中熱處理 來代替在含氮氣體環境中之Si層表面的熱處理以外’係使 用與實施例3同樣的程序實施。 (熱處理條件） •壤境氣體：Ar氣、流量17sccm 32 201131615 •氣體環境壓力：0.1mTorr(1.3xl0_2Pa) •熱處理溫度：140°C •熱處理時間：600sec 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，無法確認在Mo/Si多層反射膜的最上層亦即Si層與保護 層14之間形成有中間層13，而在Si層與保護層14的積層體 之氮含有率為0%。 (2) 表面粗糖度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗縫度。保護層丨4的表面 粗糖度rms為0.15nm。 (3) 耐洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。在 該處理的前後對保護層14表面照射E u v光(波長丨3,5 n m)，且 使用EUV反射率計（AIXUV公司製MBR(製品名）)測定EUv 反射率。在該處理的前後之Euv反射率的降低為2 9%。從 該結果，確認相較於實施例丨〜4的£1；¥1^用多層膜鏡比較 例4的EUVL用多層骐鏡係耐洗淨性差。 33 201131615 (4)财加熱處理性 對EUVL·用多層膜鏡，在210°C進行加熱處理（大氣 中）10分鐘。該處理前後的EUV反射率降低係7.8%。 從該結果，確認相較於實施例1〜4的EUVL用多層膜 鏡，比較例4的EUVL用多層膜鏡係耐加熱處理性差。 (比較例5) 比較例5係除了將S i層表面在含氮氣體環境中（氮氣與 氬氣的混合氣體環境中）進行熱處理之前，曝露在大氣中以 外，係使用與實施例3同樣的程序實施。 (大氣曝露條件） •曝露氣體：大氣(N2 :約78體積％、02 :約21體積％) •氣體環境壓力：760Torr(1.0xl05Pa) •氣體環境溫度：2(TC •曝露時間：600sec (熱處理條件） •環境氣體：Ar氣（載氣）、流量17sccm。氮氣、流量 50sccm •氮氣分壓：〇.2mTorr(2.6xl(T2Pa) •氣體環境壓力：〇.3mTorr(3.5xl(T2Pa) •熱處理溫度：140°C •熱處理時間：600sec •氮分壓X熱處理時間（在含氮氣體環境之曝露時間）： 1.2xl06L(lL(Langmuir)=lxl0'6Torr · s=l.33xlO'4Pa · s) 對按照上述程序所得到的EUVL用多層膜鏡實施下述 34 201131615 的評價。 (1) 膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 成，確認係在Mo/Si多層反射膜的最上層亦即Si層與保護層 14之間形成有中間層13。中間層13的組成係氧4at°/〇、氮 1 at%、Si95at%。又，中間層13的膜厚度為1 nm。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗糙度rms為0.15nm。 (3) 耐洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計600秒。在 該處理的前後對保護層14表面照射EUV光（波長13.5nm)，且 使用EUV反射率計（AIXUV公司製MBR(製品名）)測定EUV 反射率。在該處理的前後之EUV反射率的降低為0.8°/。。從 該結果，確認相較於實施例1〜4的EUVL用多層膜鏡，比較 例5的EUVL用多層膜鏡係耐洗淨性差。 (4) 耐加熱處理性 對EUVL用多層膜鏡，在21(TC進行加熱處理（大氣 中）10分鐘。該處理前後的EUV反射率降低係8·1%。 從該結果，確認相較於實施例1〜4的EUVL用多層膜 35 201131615 鏡，比較例5的EUVL用多層膜鏡係耐加熱處理性差。 (實施例5) 實施例5係除了在將Μ 〇/ S i多層反射膜的最上層亦即S i 層曝露在含氮氣體環境（氮氣與氬氣的混合氣體）時，依照以 下條件且不實施RF放電而對Si層表面照射紫外線以外，係 與實施例1實施同樣的程序。 (曝露條件） •載氣：Ar氣、流量17sccm •曝露氣體：氣氣、流量50sccm •氮氣分壓：〇.2mTorr(2.6xl(T2Pa) •氣體環境壓力：〇.3mTorr(3_5xl(T2Pa) •氣體環境溫度：20°C •曝露時間：600sec •曝露量：l_2xl06L(lL(Langmuir)=lxl〇-6Torr· s=1.33 xl〇*4Pa · s) •紫外線照射光源：氬準分子燈 •紫外線波長：126nm •燈窗（氟化鎂）〜基板間距離：5cm 對按照上述程序所得到的EUVL用多層膜鏡實施下述 的評價。 (1)膜組成 藉由使用X射線光電子分光裝置（X-ray Photoelectron Spectrometer)(Ulvac-phi公司製：Quantera SXM)來測定從保 護層14的表面至反射層（Mo/Si多層反射膜）12之深度方向組 36 201131615 成，確認係在Mo/Si多層反射膜的最上層亦即&層與保護層 14之間形成有中間層13。中間層13的組成係氮8心/〇、 Si92at0/。。又’中間層13的膜厚度為1ηΐΏ。 (2) 表面粗糙度 依照JIS-B0601(1994年）並使用原子間力顯微鏡 (Atomic Force Microscope)(Seiko Instruments公司製：號碼 SPI3800)來確認保護層14的表面粗糙度。保護層14的表面 粗糖度rms為0.15nm。 (3) 对洗淨性 使用臭氧水將保護層14表面旋轉洗淨處理計6〇〇秒。在 該處理的前後對保護層14表面照射EUV光（波長13.5nm)，且 使用EUV反射率計（AIXUV公司製MBR(製品名）)測定EUV 反射率。在該處理的前後之EUV反射率的降低為0.3%。 (4) 耐加熱處理性 對EUVL用多層膜鏡，在210°C進行加熱處理（大氣 中）1〇分鐘。該處理前後的EUV反射率降低係3.7%。 產業上之可利用性 因為本發明的EUV微影術用多層膜鏡係能夠抑制EUV 光線反射率低落，因此能夠有效地利用於製造半導體積體 電路，特別是能夠以高生產效率製造具有微細圖案之半導 體積體電路。 而且’將2009年12月9日申請之日本特許出願 2009-279371號、2009年12月25日申請之日本特許出願 2009-294310號、2010年2月3日申請之日本特許出願 37 201131615 2010-21944號、2010年3月24日申請之日本特許出願 2010-067421號、2010年6月14日申請之日本特許出願 2010-134822號之說明書、申請專利範圍、圖式及摘要的全 部内容引用於此，並併入作為本發明的揭示。 I；圖式簡單說明：！ 第1圖係顯示本發明EUVL用多層膜鏡的實施形態之概 略剖面圖。 【主要元件符號說明】 1...EUVL用多層膜鏡 13...中間層 11…基板 14…保護層 12…反射層 38• RF energy: 500W 29 201131615 The following evaluation was performed on the multilayer film mirror for EUVL obtained in accordance with the above procedure. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction composition, it is not confirmed that the intermediate layer 13 is formed between the Si layer and the protective layer 14 in the uppermost layer of the Mo/Si multilayer reflective film, and the nitrogen content is 0 in the laminated body of the Si layer and the protective layer 14. %. (2) Surface roughness The surface roughness of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments Co., Ltd.: number SPI3800). The surface of the protective layer 14 has a rough rms of 0.15 nm. (3) Washing resistance The surface of the protective layer 14 was rotated and washed for 600 seconds using ozone water. The surface of the protective layer 14 was irradiated with EUV light (wavelength I3.5 nm) before and after the treatment, and the EUV reflectance was measured using an EUV reflectometer. The EUV reflectance reduction before and after the treatment was 2.9%. From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 2 was inferior in washability compared to the multilayer film for EUVL of Examples 1 to 4. (4) Resistance to heat treatment The multilayer film mirror for EUVL was heat-treated at room temperature (atmosphere) for 10 minutes. The EUV reflectance reduction before and after this treatment was 7.8%. From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 2 was inferior in heat treatment resistance compared to the multilayer film for EUVL of Example 丨4. (Comparative Example 3) Comparative Example 3 was carried out in the same manner as in Example 1 except that the surface of the Si layer was not subjected to heat treatment and RF discharge was not performed, and exposure was carried out under the following exposure conditions. After the Mo/Si multilayer reflective film is formed, it is not exposed to the atmosphere, but the surface of the uppermost Si layer of the Mo/Si multilayer reflective film is mixed in a nitrogen-containing atmosphere (nitrogen and argon gas) according to the following conditions. Exposure in the environment. (Exposure conditions) • Ambient gas: Ar gas (carrier gas), flow rate 17sccm. Nitrogen, flow rate 50sccm • Nitrogen partial pressure: 〇.2mTorr (2_6xl (T2Pa) • Gas ambient pressure: 〇.3mTorr (3.5xlO_2Pa) • Heat treatment temperature: 20°C • Heat treatment time: 600sec For EUVL obtained according to the above procedure The multilayer film was subjected to the following evaluation: (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer by using an x-ray photoelectron spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction composition of the (Mo/Si multilayer reflective film) 12, it was not confirmed that the intermediate layer 13 was formed between the uppermost layer of the Mo/Si multilayer reflective film, that is, between the layer and the protective layer 14, and the Si layer and the protective layer 14 were formed. The nitrogen content of the layered body 31 201131615 is ο. 2%. (2) The surface roughness is in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (Seiko Instruments: number SPI3800). The surface roughness of the protective layer 14 was confirmed. The surface roughness rms of the protective layer 14 was 0 to 15 nm. (3) Washability The surface of the protective layer 14 was spin-washed using ozone water for 6 sec. & Front and rear protection The surface of the layer 14 was irradiated with EUV light (wavelength: π. 5 nm), and the Euv reflectance was measured using an EUV reflectance meter (MBR (product name) manufactured by AIXUV Co., Ltd.). The EUV reflectance before and after the treatment was reduced by 丨.9%. From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 3 was inferior in the detergency compared to the multilayer film mirror for EUVL of Examples 1 to 4. (4) The multilayer heat treatment film for EUVL was heat-treated. The heat treatment (in the atmosphere) was carried out at 210 ° C for 1 minute. The EUV reflectance before and after the treatment was reduced by 7.4%. From the results, it was confirmed that the EUVL was compared with the multi-wide mirrors of the examples 1 to 4 The multilayer film mirror of the EUVL of Example 3 was inferior in heat treatment property. (Comparative Example 4) Comparative Example 4 was heat-treated in an Ar gas atmosphere in place of the heat treatment of the surface of the Si layer in a nitrogen-containing gas atmosphere in accordance with the following conditions. 'Use the same procedure as in Example 3. (Heat treatment conditions) • Soil gas: Ar gas, flow rate 17sccm 32 201131615 • Gas ambient pressure: 0.1mTorr (1.3xl0_2Pa) • Heat treatment temperature: 140°C • Heat treatment time: 600sec for the EUVL obtained according to the above procedure The film was subjected to the following evaluation. (1) The film composition was measured from the surface of the protective layer 14 to the reflective layer by using an X-ray Photoelectron Spectrometer (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM). In the depth direction composition of the Mo/Si multilayer reflective film 12, it is not confirmed that the intermediate layer 13 is formed between the uppermost layer of the Mo/Si multilayer reflective film, that is, the Si layer and the protective layer 14, and the Si layer and the protective layer 14 are formed. The nitrogen content of the laminate was 0%. (2) Surface roughness The surface roughness of the protective layer 14 was confirmed in accordance with JIS-B0601 (1994) using an Atomic Force Microscope (manufactured by Seiko Instruments: number SPI3800). The surface roughness rms of the protective layer 丨4 was 0.15 nm. (3) Washing resistance The surface of the protective layer 14 was spin-washed using ozone water for 6 seconds. The surface of the protective layer 14 was irradiated with Eu v light (wavelength 丨 3, 5 n m) before and after the treatment, and the EUv reflectance was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV Co., Ltd.). The Euv reflectance reduction before and after the treatment was 2 9%. From the results, it was confirmed that the multilayer lenticular system of EUVL for Comparative Example 4 was inferior in washability as compared with the case of Example 丨~4; £1; 33 201131615 (4) Financial heat treatment property The EUVL· multilayer film mirror was heat-treated (atmosphere) at 210 ° C for 10 minutes. The EUV reflectance reduction before and after this treatment was 7.8%. From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 4 was inferior in heat treatment resistance compared to the multilayer film for EUVL of Examples 1 to 4. (Comparative Example 5) Comparative Example 5 was carried out in the same manner as in Example 3 except that the surface of the Si layer was exposed to the atmosphere before heat treatment in a nitrogen-containing gas atmosphere (in a mixed gas atmosphere of nitrogen gas and argon gas). Program implementation. (Atmospheric exposure conditions) • Exposure gas: Atmosphere (N2: about 78 vol%, 02: about 21 vol%) • Gas ambient pressure: 760 Torr (1.0 x 105 Pa) • Gas ambient temperature: 2 (TC • Exposure time: 600 sec (heat treatment) Conditions) • Ambient gas: Ar gas (carrier gas), flow rate 17sccm, nitrogen gas, flow rate 50sccm • Nitrogen partial pressure: 〇.2mTorr (2.6xl (T2Pa) • Gas ambient pressure: 〇.3mTorr (3.5xl (T2Pa) • Heat treatment Temperature: 140 ° C • Heat treatment time: 600 sec • Nitrogen partial pressure X heat treatment time (exposure time in a nitrogen-containing atmosphere): 1.2×l06L (lL (Langmuir) = lxl0'6 Torr · s = l.33xlO'4Pa · s) The following evaluation of 34 201131615 was carried out on the multilayer film mirror for EUVL obtained according to the above procedure. (1) The film composition was obtained by using an X-ray photoelectron spectrometer (Ulvac-phi company: Quantera SXM) The composition from the surface of the protective layer 14 to the depth direction of the reflective layer (Mo/Si multilayer reflective film) 12 was measured, and it was confirmed that the uppermost layer of the Mo/Si multilayer reflective film, that is, the intermediate layer between the Si layer and the protective layer 14 was formed. Layer 13. The composition of the intermediate layer 13 is oxygen 4 at ° /〇, nitrogen 1 at%, Si95at%. Further, the film thickness of the intermediate layer 13 is 1 nm. (2) Surface roughness according to JIS-B0601 (1994) and using an Atomic Force Microscope (Seiko) The surface roughness of the protective layer 14 was confirmed by the company's number: SPI3800. The surface roughness rms of the protective layer 14 was 0.15 nm. (3) Washability The surface of the protective layer 14 was rotated and washed using ozone water. EUV light (wavelength 13.5 nm) was irradiated to the surface of the protective layer 14 before and after the treatment, and EUV reflectance was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV Co., Ltd.) EUV reflection before and after the treatment From the results, it was confirmed that the multilayer film mirror for EUVL of Comparative Example 5 was inferior in washability compared to the multilayer film mirror for EUVL of Examples 1 to 4. (4) Heat resistance treatment For the EUVL multi-layered mirror, the heat treatment (atmosphere) was performed for 21 minutes at TC. The EUV reflectance before and after the treatment was reduced by 8.1%. From the results, it was confirmed that compared with Examples 1 to 4 EUVL multilayer film 35 201131615 mirror, comparative example 5 EUVL multilayer film mirror system heat resistant Poor handling. (Embodiment 5) Embodiment 5 is based on the following conditions except that the uppermost layer of the Μ 〇 / S i multilayer reflective film, that is, the S i layer, is exposed to a nitrogen-containing gas atmosphere (a mixed gas of nitrogen and argon) The same procedure as in Example 1 was carried out except that the surface of the Si layer was irradiated with ultraviolet rays by RF discharge. (Exposure conditions) • Carrier gas: Ar gas, flow rate 17sccm • Exposure gas: gas, flow rate 50sccm • Nitrogen partial pressure: 〇.2mTorr (2.6xl (T2Pa) • Gas ambient pressure: 〇.3mTorr (3_5xl (T2Pa) • Gas ambient temperature: 20 ° C • Exposure time: 600 sec • Exposure: l_2xl06L (lL (Langmuir) = lxl 〇 -6 Torr · s = 1.33 xl 〇 * 4Pa · s) • UV irradiation source: Argon excimer lamp • UV wavelength : 126 nm • Lamp window (magnesium fluoride) - distance between substrates: 5 cm The following evaluation was performed on the multilayer film mirror for EUVL obtained by the above procedure. (1) Film composition by using an X-ray photoelectron spectroscope (X- Ray Photoelectron Spectrometer) (manufactured by Ulvac-phi Co., Ltd.: Quantera SXM) to measure the depth direction group 36 from the surface of the protective layer 14 to the reflective layer (Mo/Si multilayer reflective film) 12, and confirmed that it is in the Mo/Si multilayer reflection. An intermediate layer 13 is formed between the uppermost layer of the film, that is, the & layer and the protective layer 14. The composition of the intermediate layer 13 is nitrogen 8 〇/〇, Si92at0/. Further, the film thickness of the intermediate layer 13 is 1 ΐΏ. Surface roughness according to JIS-B0601 (1994) and use of atoms The surface roughness of the protective layer 14 was confirmed by an Atomic Force Microscope (manufactured by Seiko Instruments Co., Ltd.: SPI3800). The surface roughness rms of the protective layer 14 was 0.15 nm. (3) Protection against ozone by using ozone water The surface of the layer 14 was subjected to a surface cleaning treatment for 6 sec. The surface of the protective layer 14 was irradiated with EUV light (wavelength: 13.5 nm) before and after the treatment, and EUV was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV Co., Ltd.). Reflectance: The EUV reflectance was reduced by 0.3% before and after the treatment. (4) Heat treatment resistance The multilayer film mirror for EUVL was heat-treated at 210 ° C (in the atmosphere) for 1 minute. The EUV reflectance is reduced by 3.7%. INDUSTRIAL APPLICABILITY Since the multilayer mirror system for EUV lithography of the present invention can suppress the low reflectance of EUV light, it can be effectively utilized for manufacturing a semiconductor integrated circuit, in particular, It is possible to manufacture a semiconductor integrated circuit with a fine pattern with high productivity. Moreover, the Japanese franchise application for 2009-279371, which was applied for on December 9, 2009, and the Japanese franchise for the application on December 25, 2009 -294310, Japan's franchise application on February 3, 2010, 37, 2011, 316, 2010-21944, Japan's franchise, 2010-067421, application dated March 24, 2010, and Japan's franchise application, June 14, 2010 The entire disclosure of the specification, the patent application, the drawings, and the Abstract of the disclosure of the entire disclosure is hereby incorporated by reference. I; simple description:! Fig. 1 is a schematic cross-sectional view showing an embodiment of a multilayer film mirror for EUVL of the present invention. [Description of main component symbols] 1...Multilayer film mirror for EUVL 13...interlayer 11...substrate 14...protective layer 12...reflective layer 38
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Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2009279371 | 2009-12-09 | ||
| JP2009294310 | 2009-12-25 | ||
| JP2010021944 | 2010-02-03 | ||
| JP2010067421 | 2010-03-24 | ||
| JP2010134822 | 2010-06-14 |
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| TW099143392A TWI464529B (en) | 2009-12-09 | 2010-12-09 | EUV microfilm with anti-reflective substrate, EUV microsurgical reflective mask substrate, EUV microsurgical reflective mask and manufacturing method of the reflective substrate |
| TW99143004A TW201131615A (en) | 2009-12-09 | 2010-12-09 | Multilayer mirror for euv lithography and process for producing same |
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| TW099143392A TWI464529B (en) | 2009-12-09 | 2010-12-09 | EUV microfilm with anti-reflective substrate, EUV microsurgical reflective mask substrate, EUV microsurgical reflective mask and manufacturing method of the reflective substrate |
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| US (2) | US8580465B2 (en) |
| EP (2) | EP2511944A4 (en) |
| JP (2) | JP5673555B2 (en) |
| KR (1) | KR101699574B1 (en) |
| CN (1) | CN102687071B (en) |
| TW (2) | TWI464529B (en) |
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| TWI417647B (en) | 2006-06-08 | 2013-12-01 | Asahi Glass Co Ltd | Reflective mask blank for euv lithography and substrate with functional film for the same |
| EP2028681B1 (en) * | 2007-01-31 | 2014-04-23 | Asahi Glass Company, Limited | Reflective mask blank for euv lithography |
| EP2139026B1 (en) * | 2007-04-17 | 2012-05-30 | Asahi Glass Company, Limited | Reflective mask blank for euv lithography |
| KR20090009612A (en) * | 2007-07-20 | 2009-01-23 | 엘지디스플레이 주식회사 | Method of forming inorganic insulating layer by sputtering |
| CN101978468B (en) * | 2008-03-18 | 2013-03-20 | 旭硝子株式会社 | Reflective mask blank for EUV lithography and manufacture method thereof |
| JP5258368B2 (en) * | 2008-04-30 | 2013-08-07 | Ｈｏｙａ株式会社 | Method for manufacturing substrate with multilayer reflective film, method for manufacturing reflective mask blank, and method for manufacturing reflective mask |
| JP2009272347A (en) * | 2008-04-30 | 2009-11-19 | Toshiba Corp | Light reflecting mask, exposure apparatus, measuring method, and method of manufacturing semiconductor device |
| JP2009279371A (en) | 2008-05-22 | 2009-12-03 | Tomoji Yokui | Easy hanger |
| JP4703688B2 (en) | 2008-06-03 | 2011-06-15 | 三菱電機株式会社 | Utterance right adjustment system and utterable equipment |
| JP2010021944A (en) | 2008-07-14 | 2010-01-28 | Oki Electric Ind Co Ltd | Delay time estimation apparatus, method and program |
| JP2010067421A (en) | 2008-09-10 | 2010-03-25 | Nihon Kaiheiki Industry Co Ltd | Rotary switch |
| JP2010134822A (en) | 2008-12-08 | 2010-06-17 | Riso Kagaku Corp | Semiconductor memory device |
| WO2012014904A1 (en) * | 2010-07-27 | 2012-02-02 | 旭硝子株式会社 | Substrate provided with reflecting layer for euv lithography, and reflective mask blank for euv lithography |
-
2010
- 2010-12-09 CN CN2010800562668A patent/CN102687071B/en not_active Expired - Fee Related
- 2010-12-09 EP EP10836043.9A patent/EP2511944A4/en not_active Withdrawn
- 2010-12-09 JP JP2011545247A patent/JP5673555B2/en active Active
- 2010-12-09 TW TW099143392A patent/TWI464529B/en active
- 2010-12-09 WO PCT/JP2010/072169 patent/WO2011071126A1/en active Application Filing
- 2010-12-09 KR KR1020127012513A patent/KR101699574B1/en active IP Right Grant
- 2010-12-09 TW TW99143004A patent/TW201131615A/en unknown
- 2010-12-09 EP EP10836046.2A patent/EP2511945A4/en not_active Withdrawn
- 2010-12-09 WO PCT/JP2010/072161 patent/WO2011071123A1/en active Application Filing
- 2010-12-09 JP JP2011545249A patent/JP5699938B2/en not_active Expired - Fee Related
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2012
- 2012-04-10 US US13/443,108 patent/US8580465B2/en active Active
- 2012-05-23 US US13/478,532 patent/US8993201B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2511944A1 (en) | 2012-10-17 |
| US8580465B2 (en) | 2013-11-12 |
| EP2511945A1 (en) | 2012-10-17 |
| TW201131285A (en) | 2011-09-16 |
| JP5699938B2 (en) | 2015-04-15 |
| JPWO2011071123A1 (en) | 2013-04-22 |
| TWI464529B (en) | 2014-12-11 |
| CN102687071A (en) | 2012-09-19 |
| EP2511945A4 (en) | 2014-09-03 |
| KR101699574B1 (en) | 2017-01-24 |
| CN102687071B (en) | 2013-12-11 |
| KR20120106735A (en) | 2012-09-26 |
| US20120196208A1 (en) | 2012-08-02 |
| JP5673555B2 (en) | 2015-02-18 |
| WO2011071126A1 (en) | 2011-06-16 |
| US8993201B2 (en) | 2015-03-31 |
| US20120231378A1 (en) | 2012-09-13 |
| EP2511944A4 (en) | 2014-09-03 |
| WO2011071123A1 (en) | 2011-06-16 |
| JPWO2011071126A1 (en) | 2013-04-22 |
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